Origin of the giant Allard Lake ilmenite ore deposit (Canada) by fractional crystallization,multiple magma pulses and mixing

The late-Proterozoic Allard Lake ilmenite deposit is located in the Havre-Saint-Pierre anorthosite complex, part of the allochtonous polycyclic belt of the Grenville Province. Presently the world's largest Fe–Ti oxide deposit, it had a pre-mining amount in excess of 200 Mt at grades over 60 wt.% hemo-ilmenite. The main ore body is a funnel-shaped intrusion, measuring 1.03 × 1.10 km and 100–300 m-thick. Two smaller bodies are separated by faults and anorthosite. The ore is an ilmenite-rich norite (or ilmenitite) made up of hemo-ilmenite (Hem_22.6–29.4, 66.2 wt.% on average), andesine plagioclase (An_45–50), aluminous spinel and locally orthopyroxene. Whole-rock chemical compositions are controlled by the proportions of ilmenite and plagioclase ± orthopyroxene which supports the cumulate origin of the deposit. Ore-forming processes are further constrained by normal and reverse fractionation trends of Cr concentration in cumulus ilmenite that reveal multiple magma emplacements and alternating periods of fractional crystallization and magma mixing. Mixing of magmas produced hybrids located in the stability field of ilmenite resulted in periodic crystallization of ilmenite alone. The unsystematic differentiation trends in the Allard Lake deposit, arising from a succession of magma pulses, hybridisation, and the fractionation of hemo-ilmenite alone or together with plagioclase suggest that the deposit formed within a magma conduit. This dynamic emplacement mechanism associated with continuous gravity driven accumulation of Fe–Ti oxides and possibly plagioclase buoyancy in a fractionating ferrobasalt explains the huge concentration of hemo-ilmenite. The occurrence of sapphirine associated with aluminous spinel and high-alumina orthopyroxene (7.6–9.1 wt.% Al₂O₃) lacking exsolved plagioclase supports the involvement of a metamorphic overprint during the synchronous Ottawan orogeny, which is also responsible for strong textural equilibration and external granule of exsolved aluminous spinel due to slow cooling.     

Chemical composition and evolution of the garnets in the Astamal Fe-LREE distal skarn deposit,Qara-Dagh–Sabalan metallogenic belt,Lesser Caucasus,NW Iran

The chemistry of garnet can provide clues to the formation of skarn deposits. The chemical analyses of garnets from the Astamal Fe-LREE distal skarn deposit were completed using an electron probe micro-analyzer. The three types of garnet were identified in the Astamal skarn are: (I) euhedral coarse-grained isotropic garnets (10–30 mm across), which are strongly altered to epidote, calcite and quartz in their rim and core, with intense pervasive retrograde alteration and little variation in the overall composition (Adr_94.3–84.4 Grs_8.5–2.7 Alm_1.9–0.2) (garnet I); (II) anhedral to subhedral brecciated isotropic garnets (5–10 mm across) with minor alteration, a narrow compositional range along the growth lines (Adr_82–65.4 Grs_21.9–11.7 Alm_11.1–2.4) and relatively high Cu (up to 1997 ppm) and Ni (up to 1283 ppm) (garnet II); and (III) subhedral coarser grained garnets (> 30 mm across) with moderate alteration, weak diffusion and irregular zoning of discrete grossular-almandine-rich domains (Adr_84.2–48.8 Grs_32.4–7.6 Alm_19.9–3.5) (garnet III). In the third type, the almandine content increases with increasing grossular/andradite ratio and increasing substitutions of Al for Fe^3 +.Almost all three garnet types have been replaced by fine-grained, dark-brown allanite that is typically disseminated and has the same relief as andradite. The Cu content increases while Ni content decreases slightly towards the rim of garnet II and garnet III. Copper in garnet II is positively correlated with increasing almandine content and decreasing andradite content, indicating that the almandine structure, containing relatively more Fe^2 +, is more suitable than andradite and grossular to host divalent cations such as Cu^2 +. Nickel in garnet II is positively correlated with increasing andradite content, total Fe, and decreasing almandine content. This is because Ni^2 + substitutes for Fe^3 + in the Y (octahedral) position. There are unusual discrete grossular-almandine rich domains within andraditic garnet III, indicating the low diffusivity of Ca compared to Fe at high temperatures.     

Mineralogical evidence for crystallization conditions and petrogenesis of ilmenite-series I-type granitoids at the Baogutu reduced porphyry Cu deposit (Western Junggar,NW China): Mössbauer spectroscopy,EPM and LA-(MC)-ICPMS analyses

Primary ore-forming minerals retain geochemical signatures of magmatic crystallization information and can reveal the petrochemical conditions prevalent at the time of their formation. The Baogutu deposit is a typical reduced porphyry Cu deposit. Amphibole and biotite Fe³⁺/ΣFe ratios, minerals (feldspar, biotite, amphibole, zircon and apatite), in situ elemental and apatite Nd isotopic compositions were determined by Mössbauer spectroscopy, electron probe microanalysis, and laser ablation multiple-collection inductively coupled plasma mass spectrometry, respectively, to investigate the magma oxidation state, petrogenesis, source features, and to constrain the carbon species at magmatic stages for the intrusive phases. The results show that the primary plagioclase and amphibole in the mineralized diorite to granodiorite porphyry and post ore hornblende diorite porphyry are distinct (An_26-55 versus An_60-69; Mg-hornblende versus tschermakite). In particular, the amphibole shows distinct major and trace element compositions with light rare earth element enrichments and negative Eu anomalies in Mg-hornblende and light rare earth element depletions and no Eu anomalies in tschermakite. All the analyzed biotites are primary igneous phases with a biotite phenocryst profile showing significant variations of Zn, Cr, Sc and Sr from core to rim. These results may indicate the occurrence of mixing between two distinct magmas during mineral formation. Titanium in zircon and Si¹ in amphibole thermometries indicate that magma crystallized at >900 °C and continued to ∼650 °C. In situ apatite Nd isotope (εNd(t) = 5.6–7.6, T_DM2 = 620–460 Ma), indicate absence of significant reduced sedimentary contamination and the source of juvenile lower crust. Slightly decreasing Fe³⁺/ΣFe ratios from biotite and amphibole to whole rock indicate decreasing oxygen fugacity during magma crystallization. Recalculated biotite compositions according to Fe³⁺/ΣFe ratios indicate fO₂ values of less than Ni-NiO buffer (NNO) which show slightly lower values than that estimated according to zircon/melt distribution coefficients Ce anomalies (∼ΔNNO + 0.6). These values are consistent with the features of reduced porphyry Cu deposits. Crystallization of other mineral phases significantly affects the reliability of oxybarometer of zircon/melt distribution coefficients Eu anomalies and Mn contents in apatite. This oxidation state suggests that only CO₂ was present at the magmatic stage, and implies that CH₄ formed during CO₂ reduction occurring later hydrothermal alteration. The alteration of primary amphibole to actinolite released Ti, Al, Fe, Mn, Na and K to the fluid with later precipitation of titanite, albite and minor ilmenite and magnetite during actinolite alteration.     

Conditions for the origin of oxidized carbonate-silicate melts: Implications for mantle metasomatism and diamond formation

An experimental study on the origin of ferric and ferrous carbonate-silicate melts, which can be considered as the potential metasomatic oxidizing agents and diamond forming media, was performed in the (Ca,Mg)CO₃-SiO₂-Al₂O₃-(Mg,Fe)(Cr,Fe,Ti)O₃ system, at 6.3 GPa and 1350–1650 °C. At 1350–1450 °C and ?O₂ of FMQ + 2 log units, carbonate–silicate melt, coexisting with Fe^3 +-bearing ilmenite, pyrope-almandine and rutile, contained up to 13 wt.% of Fe₂O₃. An increase in the degree of partial melting was accompanied by decarbonation and melt enrichment with CO₂, up to 21 wt.%. At 1550–1650 °C excess CO₂ segregated as a separate fluid phase. The restricted solubility of CO₂ in the melt indicated that investigated system did not achieve the second critical point at 6.3 GPa. At 1350–1450 °C and ?O₂ close to CCO buffer, Fe^2 +-bearing carbonate–silicate melt was formed in association with pyrope-almandine and Fe^3 +-bearing rutile. It was experimentally shown that CO₂-rich ferrous carbonate-silicate melt can be an effective waterless medium for the diamond crystallization. It provides relatively high diamond growth rates (3–5 μm/h) at P,T-conditions, corresponding to the formation of most natural diamonds.     

Manganoan ilmenite as kimberlite/diamond indicator mineral

Manganoan ilmenite was identified in Juina, Brazil kimberlitic rocks among other megacrysts. It forms oval, elongated, rimless grains comprising 8–30 wt.% of the heavy fraction. Internally the grains are homogeneous. The chemical composition of Mn-ilmenite is almost stoichiometric for ilmenite except for an unusually high manganese content, with MnO = 0.63–2.49 wt.% (up to 11 wt.% in inclusions in diamond) and an elevated vanadium admixture (V₂O₃ = 0.21–0.43 wt.%). By the composition, Mn-ilmenite megacrysts and inclusions in diamond are almost identical. The concentrations of trace elements in Mn-ilmenite, compared to picroilmenite, are much greater and their variations are very wide. Chondrite-normalized distribution of trace elements in Mn-ilmenite megacrysts is similar to the distribution in Mn-ilmenites included in diamond. This confirms that Mn-ilmenite in kimberlites is genetically related to diamond. The finds of Mn-ilmenite known before in kimberlitic and related rocks are late- or postmagmatic, metasomatic phases. They either form reaction rims on grains of picroilmenite or other ore minerals, or compose laths in groundmass. In contrast to those finds, Mn-ilmenite megacrysts in Juina kimberlites are a primary mineral phase with a homogeneous internal structure obtained under stable conditions of growth within lower mantle and/or transition zone. In addition to pyrope garnet, chromian spinel, picroilmenite, chrome-diopside, and magnesian olivine, manganoan ilmenite may be considered as another kimberlite/diamond indicator mineral.     

Geology and genesis of the post-collisional porphyry–skarn deposit at Bangpu,Tibet

Bangpu deposit in Tibet is a large but poorly studied Mo-rich (~ 0.089 wt.%), and Cu-poor (~ 0.32 wt.%) porphyry deposit that formed in a post-collisional tectonic setting. The deposit is located in the Gangdese porphyry copper belt (GPCB), and formed at the same time (~ 15.32 Ma) as other deposits within the belt (12 ~ 18 Ma), although it is located further to the north and has a different ore assemblage (Mo–Pb–Zn–Cu) compared to other porphyry deposits (Cu–Mo) in this belt. Two distinct mineralization events have been identified in the Bangpu deposit which are porphyry Mo–(Cu) and skarn Pb–Zn mineralization. Porphyry Mo–(Cu) mineralization in the deposit is generally associated with a mid-Miocene porphyritic monzogranite rock, whereas skarn Pb–Zn mineralization is hosted by lower Permian limestone–clastic sequences. Coprecipitated pyrite and sphalerite from the Bangpu skarn yield a Rb–Sr isochron age of 13.9 ± 0.9 Ma. In addition, the account of garnet decreases and the account of both calcite and other carbonate minerals increases with distance from the porphyritic monzogranite, suggesting that the two distinct phases of mineralization in this deposit are part of the same metallogenic event.Four main magmatic units are associated with the Bangpu deposit, namely a Paleogene biotite monzogranite, and Miocene porphyritic monzogranite, diabase, and fine-grained diorite units. These units have zircon U–Pb ages of 62.24 ± 0.32, 14.63 ± 0.25, 14.46 ± 0.38, and 13.24 ± 0.04 Ma, respectively. Zircons from porphyritic monzogranite yield ε_Hf(t) values of 2.2–8.7, with an average of 5.4, whereas the associated diabase has a similar ε_Hf(t) value averaging at 4.7. The geochemistry of the Miocene intrusions at Bangpu suggests that they were derived from different sources. The porphyritic monzogranite has relatively higher heavy rare earth element (HREE) concentrations than do other ore-bearing porphyries in the GPCB and plots closer to the amphibolite lithofacies field in Y–Zr/Sm and Y–Sm/Yb diagrams. The Bangpu diabase contains high contents of MgO (> 7.92 wt.%), FeOt (> 8.03 wt.%) but low K₂O (< 0.22 wt.%) contents and with little fractionation of the rare earth elements (REEs), yielding shallow slopes on chondrite-normalized variation diagrams. These data indicate that the mineralized porphyritic monzogranite was generated by partial melting of a thickened ancient lower crust with some mantle components, whereas the diabase intrusion was directly derived from melting of upwelling asthenospheric mantle. An ancient lower crustal source for ore-forming porphyritic monzogranite explains why the Bangpu deposit is Mo-rich and Cu-poor rather than the Cu–Mo association in other porphyry deposits in the GPCB because Mo is dominantly from the ancient crust.The Bangpu deposit has alteration zonation, ranging from an inner zone of biotite alteration through silicified and phyllic alteration zones to an outer propylitic alteration zone, similar to typical porphyry deposits. Some distinct differences are also present, for example, K-feldspar alteration at Bangpu is so dispersed that a distinct zone of K-feldspar alteration has not been identified. Hypogene mineralization at Bangpu is characterized by the early-stage precipitation of chalcopyrite during biotite alteration and the late-stage deposition of molybdenite during silicification. Fluid inclusion microthermometry indicates a change in ore-forming fluids from high-temperature (320 °C–550 °C) and high-salinity (17 wt.%–67.2 wt.%) fluids to low-temperature (213 °C–450 °C) and low-salinity (7.3 wt.%–11.6 wt.%) fluids. The deposit has lower δD_V-SMOW (− 107.1‰ to − 185.8‰) values compared with other porphyry deposits in the GPCB, suggesting that the Bangpu deposit formed in a shallower setting and is associated with a more open system than is the case for other deposits in this belt. Sulfides at Bangpu yield δ³⁴S_V-CDT values of − 2.3‰ to 0.3‰, indicative of mantle-derived S implying that coeval mantle-derived mafic magma (e.g., diabase) simultaneously supplied S and Cu to the porphyry system at Bangpu. In comparison, the Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.79–19.28, ²⁰⁷Pb/²⁰⁴Pb = 15.64–15.93, ²⁰⁸Pb/²⁰⁴Pb = 39.16–40.45) of sulfides show that other metals (e.g., Mo, Pb, Zn) were likely derived mainly from an ancient crustal source. Therefore, the formation of the Bangpu deposit can be explained by a two-stage model involving (1) the partial melting of an ancient lower crust triggered by invasion of asthenospheric mantle-derived mafic melts that provide heat and metal Cu and (2) the formation of the Bangpu porphyry Mo–Cu system, formed by magmatic differentiation in the overriding crust in a post-collisional setting.     

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.     

Isotopic (C–O–S) geochemistry and Re–Os geochronology of the Haobugao Zn–Fe deposit in Inner Mongolia,NE China

The Haobugao Zn–Fe deposit is a typical skarn deposit located in the southern part of the Great Xing’an Range that hosts polymetallic mineralization over a large region. The main ore minerals at the deposit include sphalerite, magnetite, galena, chalcopyrite and pyrite, and the main gangue minerals include andradite, grossular garnet, hedenbergite, diopside, ilvaite, calcite and quartz. There are broadly two mineralizing periods represented by the relatively older skarn and younger quartz–sulfide veins. In detail, there are five metallogenic stages consisting of an early skarn, late skarn, oxide, early quartz–sulfide, and late quartz–sulfide–calcite stages. Electron microprobe analyses show that the garnet at the deposit varies in composition from And_97.95Gro_0.41Pyr_1.64 to And_30.69Gro_66.69Pyr_2.63, and pyroxene is compositionally in the diopside–hedenbergite range (i.e. Di_90.63Hd_8.00Jo_1.37–Hd_88.98Di_4.53Jo_6.49). Petrographic observations and electron microprobe analyses indicate that the sphalerite has three generations ([Zn_0.93Fe_0.08]S–[Zn_0.75Fe_0.24]S). The Zn associated with the first generation sphalerite replaced Cu and Fe of early xenomorphic granular chalcopyrite (i.e. [Cu_1.01Fe_1.03]S₂–[Cu_0.99Fe_0.99]S₂), and part of the first generation sphalerite is coeval with late chalcopyrite (i.e. [Cu_0.96Fe_0.99Zn_0.03]S₂–[Cu_1.00Fe_1.03Zn_0.01]S₂). Magnetite has a noticeable negative Ce anomaly (δCe = ∼0.17 to 0.54), which might be a result of the oxidized ore-fluid. Thirty δ³⁴S_V-PDB analyses of sulfides from the ore range from −2.3 to −0.1‰ in value, which are indicative of a magmatic source. The δ¹³C‰ and δ¹⁸O‰ values for calcite from the ore formed at quartz–sulfide–calcite stage vary from −9.9 to −5.5‰ and from −4.2 to 1.1‰, respectively, contrasting with δ¹³C‰ (2.9–4.8‰) and δ¹⁸O‰ (9.8–13.9‰) values for calcite from marble. It is suggested that the ore-forming fluid associated with late stage of mineralization was predominantly magmatic in origin with some input of local meteoric water.Molybdenite from the Haobugao deposit defines an isochron age of 142 ± 1 Ma, which is interpreted as the mineralization age being synchronous, within error, with the zircon U–Pb ages of 140 ± 1, 141 ± 2, and 141 ± 1 Ma for granite at the deposit. These data and characteristics of lithology and mineralization further show that the Zn–Fe mineralization is temporally and spatially related to the emplacement of granite in an extensional tectonic setting during the Mesozoic.     

Geochemical features of the Matomb alluvial rutile from the Neoproterozoic Pan-African belt,Southern Cameroon

The Matomb region constitutes an important deposit of detrital rutile. The rutile grains are essentially coarse (> 3 mm), tabular and elongated, due to the short sorting of highly weathered detritus. This study reports the major, trace, and rare-earth element distribution in the bulk and rutile concentrated fractions. The bulk sediments contain minor TiO₂ concentrations (1–2 wt%), high SiO₂ contents (∼77–95 wt%) and variable contents in Al₂O₃, Fe₂O₃, Zr, Y, Ba, Nb, Cr, V, and Zn. The total REE content is low to moderate (86–372 ppm) marked by high LREE-enrichment (LREE/HREE ∼5–25.72) and negative Eu anomalies (Eu/Eu^* ∼0.51–0.69). The chemical index of alteration (CIA) shows that the source rocks are highly weathered, characteristic of humid tropical zone with the development of ferrallitic soils. In the concentrated fractions, TiO₂ abundances exceed 94 wt%. Trace elements with high contents include V, Nb, Cr, Sn, and W. These data associated with several binary diagrams show that rutile is the main carrier of Ti, V, Nb, Cr, Sn, and W in the alluvia. The REE content is very low (1–9 ppm) in spite of the LREE-abundance (LREE/HREE ∼4–40). The rutile concentrated fractions exhibit anomalies in Ce (Ce/Ce^* ∼0.58 to 0.83; ∼1.41–2.50) and Eu (Eu/Eu^* ∼0.42; 1.20–1.64). The high (La/Sm)_N, (La/Yb)_N and (Gd/Yb)_N ratios indicate high REE fractionation.     

Solubility of Fe2(OH)3Cl (pure-iron end-member of hibbingite) in NaCl and Na2SO4 brines

Pure-iron end-member hibbingite, Fe₂(OH)₃Cl(s), may be important to geological repositories in salt formations, as it may be a dominant corrosion product of steel waste canisters in an anoxic environment in Na–Cl- and Na–Mg–Cl-dominated brines. In this study, the solubility of Fe₂(OH)₃Cl(s), the pure-iron end-member of hibbingite (Fe^II, Mg)₂(OH)₃Cl(s), and Fe(OH)₂(s) in 0.04 m to 6 m NaCl brines has been determined. For the reactionFe₂(OH)₃Cl(s) + 3H⁺ ? 3 H₂O + 2 Fe²⁺ + Cl^?,the solubility constant of Fe₂(OH)₃Cl(s) at infinite dilution and 25 °C has been found to be log₁₀ K = 17.12 ± 0.15 (95% confidence interval using F statistics for 36 data points and 3 parameters). For the reactionFe(OH)₂(s) + 2H⁺ ? 2 H₂O + Fe²⁺,the solubility constant of Fe(OH)₂ at infinite dilution and 25 °C has been found to be log₁₀ K = 12.95 ± 0.13 (95 % confidence interval using F statistics for 36 data points and 3 parameters). For the combined set of solubility data for Fe₂(OH)₃Cl(s) and Fe(OH)₂(s), the Na⁺–Fe²⁺ pair Pitzer interaction parameter θ_{Na⁺/Fe²⁺} has been found to be 0.08 ± 0.03 (95% confidence interval using F statistics for 36 data points and 3 parameters). In nearly saturated NaCl brine we observed evidence for the conversion of Fe(OH)₂(s) to Fe₂(OH)₃Cl(s). Additionally, when Fe₂(OH)₃Cl(s) was added to sodium sulfate brines, the formation of green rust(II) sulfate was observed, along with the generation of hydrogen gas. The results presented here provide insight into understanding and modeling the geochemistry and performance assessment of nuclear waste repositories in salt formations.     

Some new data on the genesis of the Linghou Cu–Pb–Zn polymetallic deposit—Based on the study of fluid inclusions and C–H–O–S–Pb isotopes

The Linghou deposit, located near Hangzhou City of Zhejiang Province, eastern China, is a medium-sized polymetallic sulfide deposit associated with granitic intrusion. This deposit is structurally and lithologically controlled and commonly characterized by ore veins or irregular ore lenses. In this deposit, two mineralization events were identified, of which the former produced the Cu–Au–Ag orebodies, while the latter formed Pb–Zn–Cu orebodies. Silicification and calc-silicate (skarn type), phyllic, and carbonate alternation are four principal types of hydrothermal alteration. The early Cu–Au–Ag and late Pb–Zn–Cu mineralizations are characterized by quartz ± sericite + pyrite + chalcopyrite + bornite ± Au–Ag minerals ± magnetite ± molybdenite and calcite + dolomite + sphalerite + pyrite + chalcopyrite + galena, respectively. Calcite clusters and calcite ± quartz vein are formed during the late hydrothermal stage.The NaCl–H₂O–CO₂ system fluid, coexisting with NaCl–H₂O system fluid and showing the similar homogenization temperatures (385 °C and 356 °C, respectively) and different salinities (16.89–21.68 wt.% NaCl eqv. and 7.70–15.53 wt.% NaCl eqv.), suggests that fluid immiscibility occurred during the Cu–Au–Ag mineralization stage and might have given rise to the ore-metal precipitation. The ore-forming fluid of the Pb–Zn–Cu mineralization mainly belongs to the NaCl–H₂O–CO₂ system of high temperature (~ 401 °C) and mid-high salinity (10.79 wt.% NaCl eqv.).Fluids trapped in the quartz-chalcopyrite vein, Cu–Au–Ag ores, Pb–Zn–Cu ores and calcite clusters yielded δ¹⁸O_H2O and δD values varying from 5.54‰ to 13.11‰ and from − 71.8‰ to − 105.1‰, respectively, indicating that magmatic fluids may have played an important role in two mineralization events. The δ¹³C_PDB values of the calcite change from − 2.78‰ to − 4.63‰, indicating that the CO₃^2 − or CO₂ in the ore-forming fluid of the Pb–Zn–Cu mineralization was mainly sourced from the magmatic system, although dissolution of minor marine carbonate may have also occurred during the ore-forming processes. The sulfide minerals have homogeneous lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb ranging from 17.958 to 18.587, ²⁰⁷Pb/²⁰⁴Pb ranging from 15.549 to 15.701, and ²⁰⁸Pb/²⁰⁴Pb ranging from 37.976 to 39.052, indicating that metallic elements of the Linghou deposit came from a mixed source involving mantle and crustal components.Based on geological evidence, fluid inclusions, and H–O–C–S–Pb isotopic data, the Linghou polymetallic deposit is interpreted as a high-temperature, skarn-carbonate replacement type. Two types of mineralization are both related to the magmatic–hydrothermal system, with the Cu–Au–Ag mineralization having a close relationship with granodiorite.     

Hydrothermal alteration and ore-forming fluids associated with gold-tellurium mineralization in the Dongping gold deposit,China

The Dongping gold deposit hosted in syenites is one of the largest hydrothermal gold deposits in China and composed of ore veins in the upper parts and altered zones in the lower parts of the ore bodies. Pervasive potassic alteration and silicification overprint the wall rocks of the ore deposit. The alteration minerals include orthoclase, microcline, perthite, quartz, sericite, epidote, calcite, hematite and pyrite, with the quartz, pyrite and hematite assemblages closely associated with gold mineralization. The phases of hydrothermal alteration include: (i) potassic alteration, (ii) potassic alteration - silicification, (iii) silicification - epidotization - hematitization, (iv) silicification - sericitization - pyritization and (v) carbonation. Mass-balance calculations in potassic altered and silicified rocks reveal the gain of K₂O, Na₂O, SiO₂, HFSEs and transition elements (TEs) and the loss of REEs. Most major elements were affected by intense mineral reactions, and the REE patterns of the ore are consistent with those of the syenites. Gold, silver and tellurium show positive correlation and close association with silicification. Fluid inclusion homogenization temperatures in quartz veins range from 154 °C to 382 °C (peak at 275 °C–325 °C), with salinities of 4–9 wt.% NaCl equiv. At temperatures of 325 °C the fluid is estimated to have pH = 3.70–5.86, log fO₂ = − 32.4 to − 28.1, with Au and Te transported as Au (HS)₂⁻ and Te₂^2 − complexes. The ore forming fluids evolved from high pH and fO₂ at moderate temperatures into moderate-low pH, low fO₂ and low temperature conditions. The fineness of the precipitated native gold and the contents of the oxide minerals (e.g., magnetite and hematite) decreased, followed by precipitation of Au- and Ag-bearing tellurides. The hydrothermal system was derived from an alkaline magma and the deposit is defined as an alkaline rock-hosted hydrothermal gold deposit.     

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 Nadun Cu–Au mineralization,central Tibet: Root of a high sulfidation epithermal deposit

A new high sulfidation epithermal Cu–Au occurrence (Nadun) has been discovered adjacent to the Cretaceous Duolong porphyry Cu–Au deposit within the Bangong–Nujiang metallogenic belt, central Tibet. The Nadun Cu–Au mineralization is hosted in a tectonic–hydrothermal breccia with advanced argillic alteration, which occurs above sandstone, associated with quartz–pyrite veins. The granodiorite porphyry with strong argillic alteration yields a zircon U–Pb age of 119.1 ± 1.3 Ma, whereas the weakly argillic granodiorite porphyry intruded into the breccia has a younger age of 116.1 ± 1.3 Ma. This indicates that Cu–Au epithermal mineralization likely occurred between ~ 116 Ma and ~ 119 Ma, consistent with the duration of magmatic–hydrothermal activity at Duolong (~ 115–118 Ma), and providing evidence that Nadun and Duolong were formed during the same event. Moreover, the Nadun and Duolong porphyries have similar Hf isotopic compositions (εHf(t) values ranging from − 8.8 to 8.1; mean = 5.0 ± 1.1, n = 32), likely indicating that the deposits are comagmatic. In addition, boiling assemblages in vapor-rich inclusions coexisting with brines occur in early stage quartz–pyrite veins, and likely record phase separation at a temperature of > 550–300 °C and pressure of 700–110 bars. Most liquid-rich fluid inclusions formed at the breccia stage show similar salinity (1.7–19.3 wt.% NaCl equiv) to vapor-rich inclusions from the underlying quartz–pyrite veins, likely indicating vapor contraction during cooling at elevated presssure. This suggests that quartz–pyrite veins may act as conduits for ore-forming fluid traveling from the porphyry to the epithermal hydrothermal system. O and H isotopic compositions (δ¹⁸O_fluid = 0.42–9.71‰ and δD = − 102 to − 66‰) suggest that ore-forming fluids are dominantly from a magmatic source with a minor addition of meteoric water at a later stage. The S and Fe isotope compositions of sulfides (δ³⁴S = − 5.9 to 0.5‰ and δ⁵⁷Fe = − 2.15 to 0.17‰) decrease from the quartz–pyrite vein to breccia ore, indicating that ore-forming fluids gradually become SO₄²-enriched and relatively oxidized. This body of evidence suggests that the Nadun Cu–Au mineralization may represent the root of a high sulfidation epithermal deposit.     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

Kimberlitic sources of super-deep diamonds in the Juina area,Mato Grosso State,Brazil

The Juina diamond field, in the 1970–80s, was producing up to 5–6 million carats per year from rich placer deposits, but no economic primary deposits had been found in the area. In 2006–2007, Diagem Inc. discovered a group of diamondiferous kimberlitic pipes within the Chapadão Plateau (Chapadão, or Pandrea cluster), at the head of a drainage system which has produced most of the alluvial diamonds mined in the Juina area. Diamonds from placer deposits and newly discovered kimberlites are identical; they have super-deep origins from the upper-mantle and transition zone. Field observations and petrographic studies have identified crater-facies kimberlitic material at seven separate localities. Kimberlitic material is represented by tuffs, tuffisites and various epiclastic sediments containing chrome spinel, picroilmenite, manganoan ilmenite, zircon and diamond. The diamond grade varies from 0.2–1.8 ct/m³. Chrome spinel has 30–61 wt.% Cr₂O₃. Picroilmenite contains 6–14 wt.% MgO and 0.2–4 wt.% Cr₂O₃. Manganoan ilmenite has less than 3 wt.% MgO and 0.38–1.41 wt.% MnO. The ¹⁷⁶Hf/¹⁷⁷Hf ratio in kimberlitic zircons is 0.028288–0.28295 with ε_Hf = 5.9–8.3, and lies on the average kimberlite trend between depleted mantle and CHUR. The previously known barren and weakly diamondiferous kimberlites in the Juina area have ages of 79–80 Ma. In contrast, zircons from the newly discovered Chapadão kimberlites have a mean ²⁰⁶Pb/²³⁸U age of 93.6 ± 0.4 Ma, corresponding to a time of magmatic activity related to the opening of the southern part of the Atlantic Ocean. The most likely mechanism of the origin of kimberlitic magma is super-deep subduction process that initiated partial melting of zones in lower mantle with subsequent ascent of proto-kimberlitic magma.     

Geological characteristics and genesis of the Laoshankou Fe–Cu–Au deposit in Junggar,Xinjiang, Central Asian Orogenic Belt

The Laoshankou Fe–Cu–Au deposit is located at the northern margin of Junggar Terrane, Xinjiang, China. This deposit is hosted in Middle Devonian andesitic volcanic breccias, basalts, and conglomerate-bearing basaltic volcanic breccias of the Beitashan Formation. Veined and lenticular Fe–Cu–Au orebodies are spatially and temporally related to diorite porphyries in the ore district. Wall–rock alteration is dominated by skarn (epidote, chlorite, garnet, diopside, actinolite, and tremolite), with K–feldspar, carbonate, albite, sericite, and minor quartz. On the basis of field evidence and petrographic observations, three stages of mineralization can be distinguished: (1) a prograde skarn stage; (2) a retrograde stage associated with the development of Fe mineralization; and (3) a quartz–sulfide–carbonate stage associated with Cu–Au mineralization. Electron microprobe analysis shows that garnets and pyroxenes are andradite and diopside-dominated, respectively. Fluid inclusions in garnet yield homogenization temperatures (T_h) of 205–588 °C, and salinities of 8.95–17.96 wt.% NaCl equiv. In comparison, fluid inclusions in epidote and calcite yield T_h of 212–498 and 150–380 °C, and salinities of 7.02–27.04 and 13.4–18.47 wt.% NaCl equiv., respectively. Garnets yield values of 6.4‰ to 8.9‰ δ¹⁸O_fluid, whereas calcites yield values of − 2.4‰ and 4.2‰ δ¹⁸O_fluid, and − 0.9‰ to 2.4‰ δ¹³C_PDB, indicating that the ore-forming fluids were dominantly magmatic fluids in the early stage and meteoric water in the late stage. The δ³⁴S values of sulfides range from − 2.6‰ to 5.4‰, indicating that the sulfur in the deposit was probably derived from deep-seated magmas. The diorite porphyry yields LA–MC–ICP–MS zircon U–Pb age of 379.7 ± 3.0 Ma, whereas molybdenites give Re–Os weighted mean age of 383.2 ± 4.5 Ma (MSWD = 0.06). These ages suggest that the mineralization-related diorite porphyry was emplaced during the Late Devonian, coincident with the timing of mineralization within the Laoshankou Fe–Cu–Au deposit. The geological and geochemical evidence presented here suggest that the Laoshankou Fe–Cu–Au deposit is a skarn deposit.     

Geochemistry and magmatic history of eclogites and ultramafic rocks from the Chinese continental scientific drill hole: Subduction and ultrahigh-pressure metamorphism of lower crustal cumulates

Three distinct groups of eclogites (low-Mg–Ti eclogites, high-Ti eclogites and Mg-rich eclogites) and ultramafic rocks from the depth interval of 100–680 m of the Chinese Continental Scientific Drill Hole were studied. The low Mg#s (= 100^?molar Mg/(Mg + Fe)) (81–84%) and low Ni (1150–1220 ppm) and high Fe₂O₃^total (13–15 wt.%) contents of ultramafic rocks suggest a cumulate origin. Mg-rich eclogites show middle and heavy REE enrichments, which could not be produced by metamorphic growth of garnet. Instead, if the rocks formed from a light REE enriched magma, there may be an igneous precursor for some garnets in their protolith. Alternatively, perhaps they formed from a light REE depleted magma without garnet. The high-Ti eclogites are characterized by unusually high Fe₂O₃^total contents (up to 24.5 wt.%) and decoupling of high TiO₂ from low Nb and Ta contents. These features cannot be produced by concentration of rutile during UHP metamorphism (even for samples with TiO₂ > 4 wt.%) of high-Ti basalts, but could be attributed to crystal fractionation of titanomagnetite (for those with TiO₂ < ～ 4 wt.%) or titanomagnetite + ilmenite (for those with TiO₂ > ～ 4 wt.%). Thus, we suggest that protoliths of the high-Ti eclogites were titanomagnetite/ilmenite-rich gabbroic cumulates. As a whole, the low-Mg–Ti eclogites are geochemically complementary to the high-Ti eclogites, Mg-rich eclogites and ultramafic rocks, and could be metamorphic products of gabbroic/dioritic cumulates formed by high degree crystal fractionation. All these observations suggest that parental materials of the ultramafic rock-eclogite assemblage could represent a complete sequence of fractional crystallization of tholeiitic or picritic magmas at intermediate to high pressure, which were later carried to ultrahigh-pressure conditions during a continental collision event.     

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

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

The Variscan Tamlalt–Menhouhou gold deposit,Eastern High-Atlas,Morocco

The Tamlalt–Menhouhou gold deposit belongs to the Neoproterozoic–Palaeozoic Tamlalt inlier located in the Eastern High-Atlas (Morocco). It occurs in altered Upper Neoproterozoic bimodal volcanic and volcano-sedimentary units outcropping in the Tamlalt–Menhouhou area. Gold mineralization has been identified in quartz veins related to shear-zones associated with a strong quartz-phyllic-argillic alteration. Visible free gold is related to goethite–malachite–barite boxworks in quartz veins. The other alteration minerals accompanying gold mineralization are mainly carbonates, chlorite, hematite, albite and pyrite whose relative proportion defines three alteration types. ⁴⁰Ar/³⁹Ar geochronology performed on phengite grains from phyllic alteration and the auriferous quartz veins, yields plateau ages ranging from 300 ± 5 Ma to 284 ± 12 Ma with a weighted mean age of 293 ± 7 Ma. This identifies a Late Variscan age for the Tamlalt–Menhouhou “shear zones-related” gold deposit and emphasizes the consequences of the Variscan orogeny for gold mineralization in the High-Atlas and Anti-Atlas Neoproterozoic inliers.