Characterisation of a Natural Quartz Crystal as a Reference Material for Microanalytical Determination of Ti,Al, Li,Fe, Mn,Ga and Ge

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP‐MS, electron probe microanalysis (EPMA) and solution ICP‐MS to determine the concentration of twenty‐four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium‐in‐quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA‐ICP‐MS laboratories, three EPMA laboratories and one solution‐ICP‐MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g^?1), Al (154 ± 15 μg g^?1), Li (30 ± 2 μg g^?1), Fe (2.2 ± 0.3 μg g^?1), Mn (0.34 ± 0.04 μg g^?1), Ge (1.7 ± 0.2 μg g^?1) and Ga (0.020 ± 0.002 μg g^?1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.     

Environmental assessment of abandoned mine tailings in Adak,Västerbotten district (northern Sweden)

Sulfide-rich mine tailings in Adak that are exposed to weathering cause acid mine drainage characterized by low pH (2–4) and high SO₄ (up to 800 mg L⁻¹). Surface water, sediment and soil samples collected in this study contain higher concentrations of As, Cu, Fe and Zn, compared to the target and/or intervention limits set by international regulatory agencies. In particular, high As concentrations in water (up to 2900 μg L⁻¹) and sediment (up to 900 mg kg⁻¹) are of concern. There is large variability in trace element concentrations, implying that both physical (grain size) and chemical factors (pH, secondary phases as sulfides, Al-oxides or clay minerals) play an important role in their distribution. The low pH keeps the trace elements dissolved, and they are transported farther downstream. Trace element partition coefficients are low (log K_d = 0.3–4.3), and saturation indices calculated with PHREEQC are <0 for common oxide and sulfidic minerals. The sediment and soil samples indicate an enhanced pollution index (up to 17), and high enrichment factors for trace elements (As up to 38,300; Zn up to 800). Finally, leaves collected from different plant types indicate bioaccumulation of several elements (As, Al, Cu, Fe and Zn). However, some of the plants growing in this area (e.g., Salix, Equisétum) are generally resistant to metal toxicity, and hence, liming and phytoremediation could be considered as potential on-site remediation methods.     

Fluid inclusion geochemistry and 40Ar/39Ar geochronology constraints on the genesis of the Jianchaling Au deposit,China

The giant Jianchaling gold deposit is located in the Shaanxi Province, China. The mineralization is hosted by WNW-trending faults in the Mianxian-Lueyang-Yangpingguan (MLY) area. The mineralization can be divided into three stages based on mineralogical assemblages and crosscutting relationships of mineralized quartz veins. These stages, from early to late, are characterized by the mineral assemblage of: (1) quartz – coarse-grained pyrite – pyrrhotite – pentlandite – dolomite; (2) quartz – pyrite – gold – sphalerite – galena – carbonate – arsenopyrite – fuchsite; and (3) dolomite – calcite – quartz – fine-grained pyrite – realgar – orpiment.Three types of fluid inclusions have been recognized in this study based on petrographic and microthermometric measurements, including pure CO₂ and/or CH₄ (PC-type), NaCl-H₂O (W-type), and NaCl-CO₂-H₂O (C-type) fluid inclusions. These fluid inclusion types are present in quartz from the Stage 1 and 2 assemblages, whereas the Stage 3 quartz only contains W-type fluid inclusions. The Stage 2 assemblage is associated with the mineralization at the Jianchaling deposit. Fluid inclusions of Stage 1 quartz homogenize mainly between 250° and 360 °C, with salinities up to 15.6 wt.% NaCl equiv., whereas the Stage 3 dolomite with homogenization temperatures of 160° – 220 °C and salinities of 1.1–7.4 wt.% NaCl equiv. This indicates that the ore fluid system evolved from CO₂-rich, probably metamorphic hydrothermal to CO₂-poor, meteoric fluid. All three types of fluid inclusions can be observed in the Stage 2 quartz, suggesting that this heterogeneous association was trapped from a boiling fluid system. These inclusions homogenized at temperatures of 200°–250 °C and salinities of 1.2–12.4 wt.% NaCl equiv. The estimated trapping pressures of the fluid inclusions are between 117 and 354 MPa in Stage 1, suggesting an alternating lithostatic–hydrostatic fluid system, which was controlled by a fault-valve at the depth of ~ 12 km.Two fuchsite samples collected from the Stage 2 polymetallic-quartz veins yielded well-defined ⁴⁰Ar/³⁹Ar isotopic plateau ages of 197 ± 2 and 194 ± 2 Ma, and ³⁹Ar/³⁶Ar-⁴⁰Ar/³⁶Ar normal isochrones of 198 ± 2 and 199 ± 2 Ma. This indicates that the mineralization at Jianchaling is Early Jurassic (ca. 198 Ma) in age. We propose that Jianchaling is an orogenic gold deposit, and formed during continental collision related to the northward subduction of the Mian-Lue oceanic plate during the Early Jurassic. We also conclude that the beginning of the continental collision between the Yangtze and the North China Cratons took place around 200 Ma.     

Primary to re-equilibrated fluids and geochemical signatures for the evolution of the Nagthat siliciclastics in the Tons valley,Lesser Himalaya,India

Medium to coarse-grained Neo-Proterozoic Nagthat siliciclastic rocks form a part of the Krol Formation in the Lesser Himalayan geotectonic zone. Fluid inclusion and geochemical studies have been carried out on the Nagthat siliciclastics from the Tons valley to determine their provenance during the Proterozoic and their recrystallisation during maximum burial to uplift. Fluid inclusion studies have been carried out on detrital, recrystallised quartz grains and quartz overgrowths. Major and trace element analyses of the siliciclastics, the relationships of SiO₂ with various trace elements, and the association of various trace elements with mineral species suggest a granitic source for these siliciclastics. Primary Q1 aqueous brine inclusions and Q3 H₂O–CO₂ fluid with 0.9 gm/cm³ CO₂ density in detrital quartz grains characterised the protolith of the sandstone as granite or metamorphic rocks. H₂O–NaCl fluids participated in the cementation history, temperatures of quartz overgrowth from 198 to 232 °C show the effect of maximum burial. The re-equilibration of the primary fluid due to elevated internal pressure > confining pressure is evident from features like ‘C’ shaped cavities, stretching of the inclusions, their migration, decrepitation clusters, etc. During recrystallisation these inclusions were equilibrated at 187 ° and 235 °C in a restricted fluid of aqueous, moderately saline composition. The observed inclusion morphology is attributed to a decrease in external pressure related to isothermal decompression uplift.     

Mineral equilibria and geothermometry of the Dalaman–Köyceğiz thermal springs,southern Turkey

The Dalaman and Köyceğiz thermal springs are from karstic limestones belonging to Upper Cretaceous to Burdigalian Beydağları autochthon and Carboniferous to Lutetian Lycian nappes. They have measured temperatures of 24– 41 °C, specific electrical conductivities of 14,310–45,600 μS/cm, and are dominated by Na (1550–8500 mg/kg) and Cl (2725–15,320 mg/kg). The heat source of the geothermal systems of the area is tectonic related and the occurrence of the thermal springs is related to the young normal faults. Meteoric waters and seawaters recharge the reservoir rocks, are heated at depth with increasing geothermal gradient, and move up to the surface through the fractures and faults by convection trend and emerge as thermal springs. While thermal waters move up to the surface, they mix with different proportions of seawater and cold fresh waters. The seawater contribution to the thermal waters varies from 24% to 78%. Lake waters in the area are connected with thermal waters. Consequently, their chemical composition is influenced by the chemistry of thermal waters. Chemical equilibrium modelling based on measured outlet temperatures and measured pH shows that all the waters are oversaturated with respect to quartz and K-mica and undersaturated with respect to Al(OH)₃, anorthite, gypsum, siderite and SiO₂(a). Albite, alunite, aragonite, Ca-montmorillonite, calcite, chalcedony, chlorite, dolomite, Fe(OH)₃(a), fluorite, gypsum, illite, K-feldspar, kaolinite and sepiolite minerals are mostly oversaturated or undersaturated. Mineral saturation studies of the thermal springs indicate that dolomite, chalcedony and quartz are most likely to cause scaling at outlet conditions. Assessments from various chemical geothermometers, and Na–K–Mg ternary and mineral equilibrium diagrams suggest that the reservoir temperature is around 65–90 °C. The temperatures obtained from quartz, quartz-steam loss, Mg/Li geothermometers and mineral equilibrium diagrams give the most reasonable results.     

Laboratory study of calcite–gypsum sludge–water interactions in a flooded tailings impoundment at the Kristineberg Zn–Cu mine,northern Sweden

Due to liming of acid mine drainage, a calcite–gypsum sludge with high concentrations of Zn (24,400 ± 6900 μg g⁻¹), Cu (2840 ± 680 μg g⁻¹) and Cd (59 ± 20 μg g⁻¹) has formed in a flooded tailings impoundment at the Kristineberg mine site. The potential metal release from the sludge during resuspension events and in a long-term perspective was investigated by performing a shake flask test and sequential extraction of the sludge. The sequentially extracted carbonate and oxide fractions together contained ⩾97% of the total amount of Cd, Co, Cu, Ni, Pb and Zn in the sludge. The association of these metals with carbonates and oxides appears to result from sorption and/or coprecipitation reactions at the surfaces of calcite and Fe, Al and Mn oxyhydroxides forming in the impoundment. If stream water is diverted into the flooded impoundment, dissolution of calcite, gypsum and presumably also Al oxyhydroxides can be expected during resuspension events. In the shake flask test (performed at a pH of 7–9), remobilisation of Zn, Cu, Cd and Co from the sludge resulted in dissolved concentrations of these metals that were significantly lower than those predicted to result from dissolution of the carbonate fraction of the sludge. This may suggest that cationic Zn, Cu, Cd and Co remobilised from dissolving calcite, gypsum and Al oxyhydroxides were readsorbed onto Fe oxyhydroxides remaining stable under oxic conditions. In a long-term perspective (≳10² a), ⩾97% of the Cd, Co, Cu, Ni, Pb and Zn content of the sludge potentially is available for release by dissolution of calcite and reductive dissolution of Fe oxyhydroxides if the sludge is subject to a soil environment with lower dissolved Ca concentrations, pH and redox than in the impoundment.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

Significant Li isotope fractionation in geochemically evolved rare element-bearing pegmatites from the Little Nahanni Pegmatite Group,NWT, Canada

Lithium isotope signatures of whole rock pegmatite samples and mineral separates from the rare element-bearing Little Nahanni Pegmatite Group, NWT, and whole rock samples from nearby granitic intrusions were measured. Correlation of the Li isotopic values from the pegmatite dikes with whole rock trace element geochemistry, mineralogy and primary textural evidence reflect mechanisms of Li isotopic fractionation during pegmatite formation. The heavier δ⁷Li signatures within the broad range measured from whole rock LNPG samples (? 0.94‰ to + 11.36‰) are related to the consolidation of the final ~ 15% melt fraction of a volatile-rich peraluminous magma in the late stages of magmatic fractionation. Rock-forming minerals (quartz, albite, spodumene and mica) display δ⁷Li signatures that indicate consolidation of the dikes under variable, non-equilibrium conditions. Lithium isotope signatures of relatively cool, highly evolved peraluminous magmas reflect the build-up of fluxes (e.g., H₂O and F) and provide a qualitative assessment of the state of mineral/melt chemical equilibrium.     

Geochemistry of A-type granites in the Huangshaping polymetallic deposit (South Hunan,China): Implications for granite evolution and associated mineralization

The Huangshaping granites in Hunan Province, South China were investigated for their geochemical characteristics. Three types of granites have been petrographically identified: quartz porphyry, granophyre, and granite porphyry. Whole rock geochemistry suggests that the Huangshaping granites, especially the granite porphyry, exhibit typical A-type granite characteristics with their enrichment in Si, Rb, U, Th, and Nb and significant depletion in Ba, Sr, Ti, Eu, and P. Based on the Al, Y and Zr contents as well as the REE patterns of the rocks investigated, the quartz porphyry and the granophyre are classified as A₁ type alkaline granites whereas the granite porphyry is considered as A₂ type aluminous granite. Whole rock and quartz/feldspar O isotope data yields a wide range of δ¹⁸O_SMOW values (11.09–26.32‰). The granites are characterized by high radiogenic Pb isotopic composition. The present-day whole rock Pb isotopic ratios are ²⁰⁶Pb/²⁰⁴Pb = 18.706–19.155, ²⁰⁷Pb/²⁰⁴Pb = 15.616–15.711 and ²⁰⁸Pb/²⁰⁴Pb = 38.734–39.296. Combining the O–Pb isotope compositions with major, trace and REE geochemistry and regional geology characteristics, the Huangshaping granites were determined to resemble within-plate granites that were mainly derived from a felsic infracrustal source related to continental extension. The magma source of the quartz porphyry and the granophyre may have been generated from deeper depths, and then ascended rapidly with limited water content and low oxygen fugacity, which contributed to Cu, Pb and Zn mineralization. On the other hand, the magma that generated the granite porphyry may have ascended relatively slower and experienced pronounced crystal fractionation, upper-crustal basement rock contamination (assimilation) and wall–rock interaction, producing the Sn- and W-rich granite porphyry. This study reveals the crustal extension process and associated magmatic–metallogenic activities during 180–150 Ma in South Hunan.     

Effects of fluorine on the solubilities of Nb,Ta, Zr and Hf minerals in highly fluxed water-saturated haplogranitic melts

The effect of fluorine on the solubilities of Mn-columbite (MnNb₂O₆), Mn-tantalite (MnTa₂O₆), zircon (ZrSiO₄) and hafnon (HfSiO₄) were determined in highly fluxed, water-saturated haplogranitic melts at 800 to 1000 °C and 2 kbar. The melt composition corresponds to the intersection of the granite minimum with the albite–orthoclase tieline (Ab₇₂Or₂₈) in the quartz–albite–orthoclase system (Q–Ab–Or), which is representative of a highly fluxed melt, from which high field strength element minerals may crystallize. The melt contains 1.7 wt.% P₂O₅, 1.05 wt.% Li₂O and 1.83 wt.% B₂O₃. The main purpose of this study is to examine the effect of F on columbite, tantalite, zircon and hafnon solubility for a melt with this composition. Up to 6 wt.% fluorine was added as AgF in order to keep the aluminum saturation index (ASI, molar Al/[Na + K]) of the melt constant. In an additional experiment F was added as AlF₃ to make a glass peraluminous. The nominal ASI of the melts are close to 1 for the minimum composition and approximately 1.32 in peraluminous glasses, but if Li is considered as an alkali, the molar ratio Al/[Na + K + Li] of the melts are alkaline (0.87) and subaluminous (1.09), respectively.The molar solubility products [MnO] 1 [Nb₂O₅] and [MnO] 1 [Ta₂O₅] are nearly independent of the F content of the melt, at approximately 18.19 ± 1.2 and 43.65 ± 2.5 × 10^− 4 (mol²/kg²), respectively for the minimum composition. By contrast, there is a positive dependence of zircon and hafnon solubilities on the fluorine content in the minimum composition, which increases from 2.03 ± 0.03 × 10^− 4 (mol/kg) ZrO₂ and 4.04 ± 0.2 × 10^− 4 (mol/kg) HfO₂ for melts with 0 wt.% F to 3.81 ± 0.3 × 10^− 4 (mol/kg) ZrO₂ and 6.18 ± 0.04 × 10^− 4 (mol/kg) HfO₂ for melts with 8 wt.% F. Comparison of the data from this work and previous studies indicates that ASI of the melt seems to have a stronger effect than the contents of fluxing elements in the melt and the overall conclusion is that fluorine is less important (relative to melt compositions) than previously thought for the control on the behavior of high field strength elements in highly evolved granitic melts. Moreover, this study confirms that although Nb, Ta, Zr and Hf are all high field strength elements, Nb–Ta and Zr–Hf are complexed differently in the melt.     

Modelling of pH and inorganic aluminium after termination of liming in 3000 Swedish lakes

Significant resources are spent on counteracting the effects of acidification, mainly by liming. Due to lower S and N deposition in Europe and North America, authorities are changing directives and strategies for remediation and reducing liming. However, as the acid–base buffer capacity differs in different water bodies, the desirable reduction of the lime dose is variable. In this study, a geochemical model is used to predict pH and inorganic monomeric Al (Al_i) when liming is reduced and finally terminated in the 3000 Swedish lakes currently treated with lime. To estimate Ca and Mg concentrations not affected by liming for use in the model, the Ca/Mg ratio in nearby unlimed reference lakes was used. For the modelling of pH and inorganic Al the Visual MINTEQ program including the Stockholm Humic Model recently calibrated for Swedish fresh water was used. The predictions were validated with modelling results from six monitored lakes, in which liming had been terminated. The use of geochemical modelling appeared to be a promising tool for the calculation of accurate lime requirements in acid waters. For simulations in which liming was completely terminated, the pH value decreased by, on average, 1 pH unit to pH 5.7, whereas Al_i increased by 17 μg L⁻¹ to 32 μg L⁻¹. If liming was reduced by half, the pH would drop only 0.3 pH units and Al_i would increase by 2 μg L⁻¹. Lakes in the south-western part of Sweden were predicted to reach a lower pH and higher Al_i, which would be expected due to their greater historical S deposition. The results indicate that liming can be terminated in certain areas and in other areas be reduced without increases in the lake acidity.     

Gold mining related mercury contamination in Tongguan,Shaanxi Province,PR China

Elemental Hg–Au amalgamation mining practices are used widely in many developing countries resulting in significant Hg contamination of surrounding ecosystems. The authors examined for the first time Hg contamination in air, water, sediment, soil and crops in the Tongguan Au mining area, China, where elemental Hg has been used to extract Au for many years. Total gaseous Hg (TGM) concentrations in ambient air in the Tongguan area were significantly elevated compared to regional background concentrations. The average TGM concentrations in ambient air in a Au mill reached 18,000 ng m⁻³, which exceeds the maximum allowable occupational standard for TGM of 10,000 ng m⁻³ in China. Both total and methyl-Hg concentrations in stream water, stream sediment, and soil samples collected in the Tongguan area were elevated compared to methyl-Hg reported in artisanal Au mining areas in Suriname and the Amazon River basin. Total Hg concentrations in vegetable and wheat samples ranged from 42 to 640 μg kg⁻¹, all of which significantly exceed the Chinese guidance limit for vegetables (10 μg kg⁻¹) and foodstuffs other than fish (20 μg kg⁻¹). Fortunately, methyl-Hg was not significantly accumulated in the crops sampled in this study, where concentrations varied from 0.2 to 7.7 μg kg⁻¹.     

Elemental sulfur in drain sediments associated with acid sulfate soils

This paper reports the abundance of elemental S in drain sediments associated with acid sulfate soils. The sediments exhibited near-neutral pH (5.97–7.27), high concentrations of pore-water Fe²⁺ (1.37–15.9 mM) and abundant oxalate-extractable Fe (up to 4300 μmol g⁻¹). Maximum acid-volatile sulfide (AVS) concentrations in each sediment profile were high (118–1019 μmol g⁻¹), with AVS often exceeding pyrite-S. Elemental S occurred at concentrations of 13–396 μmol g⁻¹, with the higher concentrations exceeding previous concentrations reported for other sedimentary systems. Up to 62% of reduced inorganic S near the sediment/water interface was present as elemental S, due to reaction between AVS and oxidants such as O₂ and Fe(III). Significant correlation (r = 0.74; P < 0.05) between elemental S and oxalate-extractable Fe(III) is indicative of elemental S formation by in situ oxidation of AVS. The results indicate that AVS oxidation in near-surface sediments is dynamic in acidified coastal floodplain drains, causing elemental S to be a quantitatively important intermediate S fraction. Transformations of elemental S may therefore strongly influence water quality in ASS landscapes.     

Timing and mechanism of gold mineralization at the Wang'ershan gold deposit,Jiaodong Peninsula,eastern China

The Wang'ershan gold deposit, located in the southern Jiaojia goldfield, is currently the largest gold deposit hosted within the subsidiary faults in Jiaodong Peninsula, with a gold reserve of > 60 t gold at a grade of 4.07 g/t Au. It is hosted in the Late Jurassic Linglong biotite granites and controlled by the second-order, N- to NNE-trending Wang'ershan Fault (and its subsidiary faults) which is broadly parallel to the first-order Jiaojia Fault in the goldfield. Gold mineralization occurs as both disseminated- and stockwork-style and quartz–sulfide vein-style ores, mainly within altered cataclasites and breccias, and sericite–quartz and potassic alteration zones, respectively. Mineralization stages can be divided into (1) the pyrite–quartz–sericite stage, (2) the quartz–pyrite stage, (3) the quartz–sulfide stage, and (4) the quartz–carbonate stage.Two sericite samples associated with the main ore-stage pyrites from pyritic phyllic ores of the deposit with weighted mean plateau ⁴⁰Ar/³⁹Ar age of 120.7 ± 0.6 Ma and 119.2 ± 0.5 Ma, respectively, were selected for ⁴⁰Ar/³⁹Ar geochronology. On the basis of petrography and microthermometry, three types of primary fluid inclusions related to the ore forming event were identified: type 1 H₂O–CO₂–NaCl, type 2 aqueous, and type 3 CO₂ fluid inclusions (in decreasing abundance). Stage 1 quartz contains all three primary fluid inclusions, while stages 2 and 3 quartz contain both type 1 and 2 inclusions, and stage 4 quartz contains only type 2 inclusions. The contemporaneous trapping, similar salinities and total homogenization temperature ranges, and different homogenization phases of type 1 and type 2 inclusions indicate that fluid immiscibility did take place in stages 1, 2 and 3 ores, with P–T conditions of 190 to 85 MPa and 334 to 300 °C for stage 1 and 200 to 40 MPa and 288 to 230 °C for stages 2 and 3. Combined with the H–O–C–S–Pb isotopic compositions, ore-forming fluids may have a metamorphic-dominant mixed source, which could be associated with the dehydration and decarbonisation of a subducting paleo-Pacific plate and characterized by medium–high temperature (285–350 °C), CO₂-bearing (~ 8 mol%) with minor CH₄ (1–4% in carbonic phase), and low salinity (3.38–8.45 eq. wt.% NaCl). During mineralization, the fluid finally evolved into a medium–low temperature NaCl–H₂O system. Au(HS)₂⁻ was the most probable gold-transporting complex at Wang'ershan, due to the low temperature (157–350 °C) and near-neutral to weakly acidic ore fluids. The reaction between gold-bearing fluids and iron-bearing wall-rocks, and fluid-immiscibility processes caused via fluid–pressure cycling during seismic movement along fault zones that host lode-gold orebodies, which led to breakdown of Au(HS)₂⁻, are interpreted as the two main precipitation mechanisms of gold deposition.In general, the Wang'ershan deposit and other deposits in the Jiaojia camp have concordant structural system and wall-rock alteration assemblages, nature of orebodies and gold occurrence conditions, as well as the similar geochronology, ore-forming fluids system and stable isotope compositions. Thus gold mineralization in the Jiaojia goldfield was a large-scale unified event, with consistent timing, origin, process and mechanism.     

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.     

The influence of citric acid,EDTA, and fulvic acid on U(VI) sorption onto kaolinite

Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10^?6–1 × 10^?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO₃), and pCO₂ (0–5%) in the presence or absence of 1 × 10^?2–1 × 10^?4 M citric acid, 1 × 10^?2–1 × 10^?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10^?6–1 × 10^?4 M U(VI) in 0.01 M NaNO₃ were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10^?5 and 1 × 10^?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10^?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO₂ greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.     

In-situ LA-ICPMS trace elements and U–Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit,Daye district,China

In this paper, we present U–Pb ages and trace element compositions of titanite from the Ruanjiawan W–Cu–Mo skarn deposit in the Daye district, eastern China to constrain the magmatic and hydrothermal history in this deposit and provide a better understanding of the U–Pb geochronology and trace element geochemistry of titanite that have been subjected to post-crystallization hydrothermal alteration. Titanite from the mineralized skarn, the ore-related quartz diorite stock, and a diabase dike intruding this stock were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Titanite grains from the quartz diorite and diabase dike typically coexist with hydrothermal minerals such as epidote, sericite, chlorite, pyrite, and calcite, and display irregular or patchy zoning. These grains have low LREE/HREE and high Th/U and Lu/Hf ratios, coupled with negative Eu and positive Ce anomalies. The textural and compositional data indicate that titanite from the quartz diorite has been overprinted by hydrothermal fluids after being crystallized from magmas. Titanite grains from the mineralized skarn are texturally equilibrated with retrograde skarn minerals including actinolite, quartz, calcite, and epidote, demonstrating that these grains were formed directly from hydrothermal fluids responsible for the mineralization. Compared to the varieties from the quartz diorite stock and diabase dike, titanite grains from the mineralized skarn have much lower REE contents and LREE/HREE, Th/U, and Lu/Hf ratios. They have a weighted mean ²⁰⁶Pb/²³⁸U age of 142 ± 2 Ma (MSWD = 0.7, 2σ), in agreement with a zircon U–Pb age of 144 ± 1 Ma (MSWD = 0.3, 2σ) of the quartz diorite and thus interpreted as formation age of the Ruanjiawan W–Cu–Mo deposit. Titanite grains from the ore-related quartz diorite have a concordant U–Pb age of 132 ± 2 Ma (MSWD = 0.5, 2σ), which is 10–12 Ma younger than the zircon U–Pb age of the same sample and thus interpreted as the time of a hydrothermal overprint after their crystallization. This hydrothermal overprint was most likely related to the emplacement of the diabase dike that has a zircon U–Pb age of 133 ± 1 Ma and a titanite U–Pb age of 131 ± 2 Ma. The geochronological results thus reveal two hydrothermal events in the Ruanjiawan deposit: an early one forming the Wu–Cu–Mo ores related to the emplacement of the quartz diorite stock and a later one causing alteration of the quartz diorite and its titanite due to emplacement of diabase dike. It is suggested that titanite is much more susceptible to hydrothermal alteration than zircon. Results from this study also highlight the utilization of trace element compositions in discriminating titanite of magmatic and hydrothermal origins, facilitating a more reasonable interpretation of the titanite U–Pb ages.     

Listvenite-related gold deposits of the South Urals (Russia): A review

The Urals is a complex fold belt, which underwent long geological evolution. The formation of most gold deposits in the Urals is related to the collision stage. In this paper, we review some relatively small listvenite-related gold deposits, which are confined to the large Main Uralian fault zone and some smaller faults within the Magnitogorsk zone. The Mechnikovskoe, Altyn-Tash, and Ganeevskoe deposits are studied in detail in this contribution. They comprise the ore clusters along with other numerous small gold deposits, and constituted the sources for the gold placers exploited in historical time. The gold is hosted by metasomatites (listvenites, beresites) and quartz veins with economic gold grades (up to 20 g/t Au). Listvenites are developed after serpentinites and composed of quartz, fuchsite, and carbonates (magnesite, dolomite) ± albite. Volcanic and volcanoclastic rocks are altered to beresites, consisting of sericite, carbonates (dolomite, ankerite), quartz and albite. Pyrite and chalcopyrite are major ore minerals associated with gold; pyrrhotite, Ni sulfides, galena, sphalerite, arsenopyrite and Au-Ag tellurides are subordinate and rare. Gold in these deposits is mostly high-fineness (>900‰). The lower fineness (∼800‰) is typical of gold in assemblage with polymetallic sulfides and tellurides. The ores have been formed from the NaCl–CO₂–H₂O ± CH₄ fluids of low (∼2 wt% NaCl-equiv.) to moderate (8–16 wt% NaCl-equiv.) salinity at temperatures of 210–330 °C. The oxygen isotopic composition of quartz (δ¹⁸O) varies from 14.7 to 15.4‰ (Mechnikovskoe deposit), 13.2 to 13.6‰ (Altyn-Tash deposit) and 12.0 to 12.7‰ (Ganeevskoe deposit). The oxygen isotopic composition of albite from altered rocks of the Ganeevskoe deposit is 10.1‰. The calculated δ¹⁸O_H2O values of the fluid in equilibrium with quartz are in a range of 5.7–6.3, 4.2–4.6 and 6.3–6.7‰ respectively, and most likely indicate a magmatic fluid source.     

Petrogenesis of granitoids in the Dewulu skarn copper deposit: implications for the evolution of the Paleotethys ocean and mineralization in Western Qinling,China

The Tethyan tectonic domain hosts numerous world-class mineral deposits. Among these, the Dewulu skarn copper deposit in Western Qinling, China belongs to the Paleotethys ore belt. The skarn and orebodies here occur as stratoids or lenses at the contact between the Triassic Dewulu intrusive complex and Permian marine clastic and carbonates. Alteration minerals include prograde skarns (garnet, diopside, wollastonite), plagioclase, hornblende, actinolite, tremolite, epidote, chlorite, calcite, quartz and sericite. The main ore types include early disseminated skarn-type replacement orebodies and late-stage quartz-sulfide veins. Chalcopyrite is the major ore mineral, along with pyrite, bornite and sphalerite. The Dewulu intrusive complex comprises quartz diorite, quartz diorite porphyry and dioritic mafic microgranular enclaves (MME). The MMEs are spheroidal in shape, and have igneous mineral assemblages, acicular apatites, complex oscillatory zoned plagioclase and quartz megacrysts surrounded by mafic minerals. The MMEs are metaluminous and calc-alkaline to high-K calc-alkaline, and possess relatively high Ni, Cr and MgO contents and Mg^# values. They display sub-parallel patterns in trace element spider diagrams and rare earth element (REE) plots. They are also characterized by the enrichment of Rb, U and Th, depletion of Ba, Sr, Nb and Ta and negative Eu anomaly. Zircon LA-ICP-MS U–Pb dating of the dioritic MME yields an age of 247.0 ± 2.2 Ma, coeval with the host quartz diorite, quartz diorite porphyry and ore-related sericite ⁴⁰Ar/³⁹Ar plateau ages within analytical uncertainties. Oxygen fugacity estimated from trace element compositions of zircons from the dioritic MME shows FMQ ± 3.3. The zircons have negative ε_Hf(t) values in a range of − 8.0 to − 3.3, corresponding to two-stage model ages ranging from 1.48 to 1.78 Ga. The integrated data from petrology, geochronology and bulk geochemistry suggest that the Early Triassic granitoids associated with Cu skarn mineralization at Dewulu were products of arc magmatism and involved magma mixing in an active continental margin setting. The magma was sourced through partial melting of enriched sub-continental lithospheric mantle that had been previously modified by slab-derived melt during the continuous northward subduction of the Paleotethys oceanic slab.     

Jurassic magmatism related Pb-Zn-W-Mo polymetallic mineralization in the central Nanling Range,South China: Geochronologic,geochemical, and isotopic evidence from the Huangshaping deposit

The Nanling Range in South China is characterized by extensive Mesozoic magmatism and coeval nonferrous and rare metal mineralization. Huangshaping is a world-class Pb-Zn-W-Mo polymetallic skarn deposit in the central Nanling Range. Magmatic rocks occurring in this ore district include quartz porphyry, granite porphyry, granophyre, dacite porphyry, and aplite, with only the first three granitoids genetically associated with polymetallic mineralization. Most of the orebodies are constrained within the contact zones as skarn and veins between these granitic stocks and the carbonate wall rocks.Since the age of the quartz porphyry is still controversial, and studies of the dacite porphyry and aplite are absent, we focus on these magmatic rocks first. LA-ICP-MS zircon U-Pb dating suggests that the crystallization ages of the quartz porphyry, dacite porphyry, and aplite are 154.3 ± 1.9 Ma, 158.1 ± 0.8 Ma, and 148.4 ± 3.4 Ma, respectively. Combined with previously published age data, we infer the evolutionary sequence of magmatic rocks should be dacite porphyry → quartz porphyry → granite porphyry (granophyre) → aplite. The quartz porphyry, dacite porphyry, and aplite yield high contents of high field strength elements (Zr + Nb + Ce + Y = 255–440 ppm), high ratios of 10,000 × Ga/Al (2.6–3.2), and prominent depletions in Ba, Sr, Eu, P, and Ti, indicating their crustal affinities to A-type granites. They have negative ε_Nd(t) values (−9.4 to −7.0) and high initial Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb_i = 18.307–18.644, ²⁰⁷Pb/²⁰⁴Pb_i = 15.689–15.742, ²⁰⁸Pb/²⁰⁴Pb_i = 38.589–38.986), suggesting that they were probably derived by partial melting of ancient granulitic crustal materials.The sulfide minerals exhibit a wide range of δ³⁴S_V-CDT values from −22.6 to 24.2‰, with ²⁰⁶Pb/²⁰⁴Pb of 17.669–19.708, ²⁰⁷Pb/²⁰⁴Pb of 15.492–15.714, and ²⁰⁸Pb/²⁰⁴Pb of 37.880–39.789, indicating that sulfur, lead, and other associated metals were derived from a mixture of magmatic components and the Carboniferous wall rocks. Fluid inclusions in pyrrhotite, sphalerite, and marmatite samples have ³He/⁴He ratios of 0.12 to 1.53 Ra, with calculated mantle helium proportions of 1.3 to 18.9%, indicating a predominantly crustal origin for the ore fluids, with minor inputs from the mantle. The Huangshaping deposit is a typical example of the genetic relationship both spatially and temporally between Jurassic magmatism and polymetallic metallogeny in the Nanling Range.