Physicochemical parameters of the formation of hydrothermal deposits: A fluid inclusion study. I. Tin and tungsten deposits

The author’s database, which presently includes data from more than 18500 publications on fluid and melt inclusions in minerals and is continuing to be appended, was used to generalize results on physicochemical parameters of the formation of hydrothermal deposits and occurrences of tin and tungsten. The database includes data on 320 tin and tin-tungsten deposits and occurrences and 253 tungsten and tungstentin deposits around the world. For most typical minerals of these deposits (quartz, cassiterite, tungsten, scheelite, topaz, beryl, tourmaline, fluorite, and calcite), histograms of homogenization temperatures of fluid inclusions were plotted. Most of 463 determinations made for cassiterite are in the range of 300–500°C with maximum at 300–400°C, while those for wolframite and scheelite (453 determinations) fall in the range of 200–400°C with maximum at 200–300°C. Representative material on pressures of hydrothermal fluids included 330 determinations for tin and 430 determinations for tungsten objects. It was found that premineral, ore, and postmineral stages spanned a wide pressure range from 70–110 bar to 6000–6400 bar. High pressures of the premineral stages at these deposits are caused by their genetic relation with felsic magmatism. Around 50% of pressure determinations lie in the range of 500–1500 bar. The wide variations in total salinity and temperatures (from 0.1 to 80 wt % NaCl equiv and 20–800°C) were obtained for mineral-forming fluids at the tin (1800 determinations) and tungsten (2070 determinations) objects. Most of all determinations define a salinity less than 10 wt % NaCl equiv. (∼60%) and temperature range of 200–400°C (∼70%). The average composition of volatile components of fluids determined by different methods is reported. Data on gas composition of the fluids determined by Raman spectroscopy are examined. Based on 180 determinations, the fluids from tin objects have the following composition (in mol %): 41.2 CO₂, 39.5 CH₄, 19.15 N₂, and 0.15 H₂S. The volatile components of tungsten deposits (190 determinations) are represented by 56.1 CO₂, 30.7 CH₄, 13.2 N₂, and 0.01 H₂S. Thus, the inclusions of tungsten deposits are characterized by higher CO₂ content and lower (but sufficiently high) contents of CH₄ and N₂. The concentrations of tin and tungsten in magmatic melts and mineral-forming fluids were estimated from analysis of individual inclusions. The geometric mean Sn contents are 87 ppm (+ 610 ppm/−76 ppm) in the melts (569 determinations) and 132 ppm (+ 630 ppm/−109 ppm) in the fluids (253 determinations). The geometric mean W values are 6.8 ppm (+ 81/−6.2 ppm) in the magmatic melts (430 determinations) and 30 ppm (+ 144 ppm/−25 ppm) in the mineral-forming fluids (391 determinations).     

An experimental study of bromine behaviour in water-saturated silicic melts

To assess the effect of the melt composition on bromine concentrations in magmas, we have investigated bromide solubility for water-saturated, iron-free silicic melts with variable Na+K/Al and Si/Al molar ratios (albite, haplogranite, rhyolite, and pantellerite). The experiments were performed in rapid quench cold-seal autoclaves over a range of pressure (1, 1.5, and 2 kbar) and temperature (900, 1000, and 1080 °C) with run durations from 5 to 7 days. A series of natural volcanic glasses and melt inclusions hosted in magmatic minerals were analysed together with the synthetic glasses by PIXE (proton-induced X-ray emission). The Br concentrations range from 5360 to 7850 ppm for albite, from 2800 to 3900 ppm for haplogranite, from 4300 to 5900 ppm for rhyolite, and from 9745 to 11,250 ppm for pantellerite. Br concentrations are negatively correlated with pressure in H₂O-saturated silicic melts and vary with (Na+K)/Al molar ratio with a minimum value at the ratio close to unity. Br behaves similarly to chlorine for all of these melt compositions. The bromide solubility is similar in albitic and rhyolitic melts, which implies that D^f/m is nearly the same for both compositions and is applicable for natural rhyolites as suggested in our previous study (Bureau et al., 2000). This means that the volcanic Br contribution to the atmosphere may be significant. In natural obsidian samples and MI hosted in quartz, olivine, and leucite, the Br concentration varies from < 3 to 28 ppm, with the highest concentrations in pantelleritic melts. We attribute the low Br concentrations of natural melts to a low initial abundance of this halogen in the Earth mantle. However, because Br behaves as an incompatible element before water exsolution, our results imply that magmas could contain much more dissolved Br before eruption and water degassing than the few ppm usually measured in volcanic rocks. Br behaviour during magma crystallisation is controlled by its partitioning into the H₂O-rich fluid phase when this occurs. In addition, its potential high solubility in silicate melts makes it a very sensitive chemical tracer of magma contamination by seawater and Br-rich material. This infers that the investigation of Br behaviour in subduction-zone samples may help for a better understanding of volatiles cycling between the Earth reservoirs.     

Physicochemical parameters of the origin of hydrothermal mineral deposits: Evidence from fluid inclusions. IV. Copper and molybdenum deposits

Physicochemical parameters of the origin of Cu and Mo deposits are reviewed based on an original database that currently includes information from more than 21000 publications on fluid and melt inclusions hosted in various minerals. The deposits are classified into three types: (i) Cu–Mo (usually porphyry), (ii) Cu (usually without Mo but often with base metals), and (iii) Mo (without Cu but often with Be and W). For these deposits, the temperature and pressure of their origin and the density, salinity, and gas composition of the fluids are discussed. The average composition of the dominant volatile components of natural fluids is reported for Cu and Mo deposits and is compared with the composition of volatiles in fluids at Au, Sn, W, Pb, and Zn deposits. Data on individual inclusions are used to evaluate the Cu and Mo concentrations in the magmatic silicate melts and mineral-forming fluids.     

Tracing the evolution and distribution of F and Cl in plutonic systems from volatile-bearing minerals: a case study from the Liujiawa pluton (Dabie orogen, China)

Fluorine and chlorine play an important role in magmatic differentiation, hydrothermal alteration, and related mineralization processes, but tracing their evolution in magmatic and especially plutonic systems is not an easy task. The F and Cl in melts can be estimated from F and Cl concentrations in minerals, provided that partitioning between minerals and melts are constrained. Based on available partitioning models between mineral/melt, mineral/fluid, and melt/fluid, a set of equations has been derived to determine F and Cl concentrations in melts from the compositions of amphibole, biotite, and apatite. The new calculation procedure has been applied to a plutonic system, the Liujiawa pluton, eastern Dabie orogen (China). Cl and F concentrations in amphiboles, biotites, and apatites from different rock types (gabbronorite, two-pyroxene diorite, clinopyroxene diorite, and hornblende gabbro) have been determined by electron microprobe. Most amphiboles show a negative correlation between log(Cl/OH) and Mg-number and a positive correlation between log(F/OH) and A-site occupation. Biotites from the gabbronorite and two-pyroxene diorite show a slight positive correlation between log(Cl/OH) and Mg, which is however not the case for the clinopyroxene diorite. Apatites from all the samples are rich in F and show negative correlations between Cl and F concentrations. In our case study, we demonstrate that the Cl concentration in melt remains approximately constant at 1,000–2,000?ppm over the major crystallization interval, but decreases strongly at near solidus temperatures as a result of fluid exsolution. The F concentration in melt remains nearly constant at ca. 2,000–3,000?ppm at high temperatures as well as near solidus conditions, indicating that it is not largely affected by fluid exsolution because of its strongly preferred incorporation into melt. Interestingly, the evolution of Cl and F concentrations in melt with magmatic differentiation is similar to that determined in volcanic systems, suggesting that the evolution of Cl and F in melts during crystallization and late magmatic stages at depth (plutonic systems) is similar to that observed in volcanic systems during decompression and degassing.     

Silicate and salt melts in the genesis of the industrial’noe tin deposit: Evidence from inclusions in minerals

The data obtained on melt and fluid inclusions in minerals of granites, metasomatic rocks, and veins with tin ore mineralization at the Industrial’noe deposit in the southern part of the Omsukchan trough, northeastern Russia, indicate that the melt from which the quartz of the granites crystallized contained globules of salt melts. Silicate melt inclusions were used to determine the principal parameters of the magmatic melts that formed the granites, which had temperatures at 760–1020°C, were under pressures of 0.3–3.6 kbar, and had densities of 2.11–2.60 g/cm³ and water concentrations of 1.7–7.0 wt %. The results obtained on the fluid inclusions testify that the parameters of the mineral-forming fluids broadly varied and corresponded to temperatures at 920–275°C, pressures 0.1–3.1 kbar, densities of 0.70–1.90 g/cm³, and salinities of 4.0–75.0 wt % equiv. NaCl. Electron microprobe analyses of the glasses of twelve homogenized inclusions show concentrations of major components typical of an acid magmatic melt (wt %, average): 73.2% SiO₂, 15.3% Al₂O₃, 1.3% FeO, 0.6% CaO, 3.1% Na₂O, and 4.5% K₂O at elevated concentrations of Cl (up to 0.51 wt %, average 0.31 wt %). The concentrations and distribution of some elements (Cl, K, Ca, Mn, Fe, Cu, Zn, Pb, As, Br, Rb, Sr, and Sn) in polyphase salt globules in quartz from both the granites and a mineralized miarolitic cavity in granite were assayed by micro-PIXE (proton-induced X-ray emission). Analyses of eight salt globules in quartz from the granites point to high concentrations (average, wt %) of Cl (27.5), Fe (9.7), Cu (7.2), Mn (1.1), Zn (0.66), Pb (0.37) and (average, ppm) As (2020), Rb (1850), Sr (1090), and Br (990). The salt globules in the miarolitic quartz are rich in (average of 29 globules, wt %) Cl (25.0), Fe (5.4), Mn (1.0), Zn (0.50), Pb (0.24) and (ppm) Rb (810), Sn (540), and Br (470). The synthesis of all data obtained on melt and fluid inclusions in minerals from the Industrial’noe deposit suggest that the genesis of the tin ore mineralization was related to the crystallization of acid magmatic melts. Original Russian Text@ V.B. Naumov, V.S. Kamenetsky, 2006, published in Geokhimiya, 2006, No. 12, pp. 1279–1289.     

Mean concentrations of volatile components,major and trace elements in magmatic melts in major geodynamic environments on Earth. I. Mafic melts

Mean concentrations of major components, trace elements, and volatile components in magmatic melts from Earth’s major geodynamic environments are estimated using our database (which comprises more than 1200000 analyses for 75 chemical elements—state for the beginning of 2016) on melt inclusions and quench glasses of rocks). The geodynamic environments are classified into (I) environments of oceanic plate spreading (mid-oceanic ridges), (II) areas affected by mantle plumes in oceanic plates (oceanic islands and lava plateaus), (III and IV) subduction-related environments (III are magmatic zones in island arcs, and IV are magmatic zones in active continental margins, in which magma-generating processes involve the continental crust), (V) continental rifts in areas with continental hotspots, and (VI) backarc spreading zones. The distribution of SiO₂ concentrations (>71000 analyses) in natural magmatic melts in all geodynamic environments is obviously bimodal, with maxima at 50–52 and 72–76 wt % SiO₂. Herein we discuss only mafic melts (40–54 wt % SiO₂). Mean concentrations and confidence levels are calculated for each geodynamic environment for the first time in three variants: from melt inclusions in minerals, from quench glasses in rocks, and from all data. Systematic variations in the mean compositions of melt inclusions and glasses in rocks are detected for all geodynamic environments. Primitive mantle-normalized multielemental patterns for mean concentrations of elements are constructed for magmatic melts from all geodynamic environments, and the mean ratios and their variations are calculated for trace incompatible and volatile components (H₂O/Ce, K₂O/Cl, La/Y, Nb/U, Ba/Rb, Ce/Pb, etc.) in melts from all environments.     

Alkaline granites and Be (Phenakite-bertrandite) mineralization: An example of the Orot and Ermakovka deposits

The Orot (Or) and Ermakovka (Er) intrusions of aegirine granites with various resources of accompanying Be mineralization in Transbaikalia were studied to reproduce Be behavior during the crystallization and degassing of alkaline granite magma. Data on the petrography and geochemistry of the rocks and the microthermomety and microprobe analysis of fluid and melt inclusions in them indicate that the intrusions were formed by discrete magma portions derived from a single magmatic source during successive stages of its differentiation. The intrusions crystallized at temperatures higher than 1030–1070°C (Or) and 840–640°C (Er), and the melts contained elevated concentrations of H₂O and F: from 2.1 to 3.5% F and from <1 to 1% H₂O for the former intrusion and from 3.9 to 6.7% F and from <2.6 to 4.1% H₂O for the latter. Fluids were released from the magma during a late crystallization stage for the Orot intrusion and an intermediate stage for the Ermakovka intrusion. Early in the course of this process, the fluids were halide-sulfate brines with the Cl: F ratio higher for the Orot intrusion and lower for the Ermakovka intrusion. A temperature decrease resulted in the exsolution of the fluids into two immiscible phases, one of which contained low and the other high concentrations of salts. The magmatic brines and low-salinity solutions of both intrusions were enriched in Be (up to 1.1 g/kg), which is comparable with the concentration of this element in the emanations of Be-bearing pegmatites in the Pamirs and is manyfold higher than C _Be in magmatic fluids related to granite intrusions with W-Sn mineralization. The Be ore mineralization of the Orot and Ermakovka deposits was produced by solutions whose composition and Be concentrations were analogous to those in the low-salinity phase of the corresponding magmatic fluids. The brines of the Ermakovka intrusion were enriched in Mo (up to 17 g/kg) and, to a lesser extent, Mn, Ce, and La and produced uneconomic monazite-molybdenite ore mineralization. Based on available data and results of our calculations, we arrived at the conclusion that the very high alkali concentrations in the melts of both intrusions (ASI < 1), their high F concentrations (up to 4.1%), and the absence of magmatic Be-bearing minerals facilitated Be selective extraction by the separated fluids in the form of its most soluble F-complexes. The high oxidation of the melt predetermined the predominance of hexavalent S and Mo compounds, which could be efficiently extracted by the fluid phase in the form of sulfates and molybdates of alkali metals. The differences in the ore potentials of the Orot and Ermakovka intrusions were caused by the different H₂O, F, and perhaps, also Be concentrations in the parental melts, which was, in turn, caused by their different degrees of differentiation during the preintrusive stages of their magmatic evolution.     

Genesis of massive sulfide deposits in the Verkhneural’sk ore district, the South Urals, Russia: Evidence for magmatic contribution of metals and fluids

Melt inclusions and aqueous fluid inclusions in quartz phenocrysts from host felsic volcanics, as well as fluid inclusions in minerals of ores and wall rocks were studied at the Cu-Zn massive sulfide deposits in the Verkhneural’sk ore district, the South Urals. The high-temperature (850–1210°C) magmatic melts of volcanic rocks are normal in alkalinity and correspond to rhyolites of the tholeiitic series. The groups of predominant K-Na-type (K₂O/Na₂O = 0.3–1.0), less abundant Na-type (K₂O/Na₂O = 0.15–0.3), and K-type (K₂O/Na₂O = 1.9–9.3) rhyolites are distinguished. The average concentrations (wt %) of volatile components in the melts are as follows: 2.9 H₂O (up to 6.5), 0.13 Cl (up to 0.28), and 0.09 F (up to 0.42). When quartz was crystallizing, the melt was heterogeneous, contained magnetite crystals and sulfide globules (pyrrhotite, pentlandite, chalcopyrite, bornite). High-density aqueous fluid inclusions, which were identified for the first time in quartz phenocrysts from felsic volcanics of the South Urals, provide evidence for real participation of magmatic water in hydrothermal ore formation. The fluids were homogenized at 124–245°C in the liquid phase; the salinity of the aqueous solution is 1.2–6.2 wt % NaCl equiv. The calculated fluid pressure is very high: 7.0–8.7 kbar at 850°C and 5.1–6.8 kbar at 700°C. The LA-ICP-MS analysis of melt and aqueous fluid inclusions in quartz phenocrysts shows a high saturation of primary magmatic fluid and melt with metals. This indicates ore potential of island-arc volcanic complexes spatially associated with massive sulfide deposits. The systematic study of fluid inclusions in minerals of ores and wall rocks at five massive sulfide deposits of the Verkhneural’sk district furnished evidence that ore-forming fluids had temperature of 375–115°C, pressure up to 1.0–0.5 kbar, chloride composition, and salinity of 0.8–11.2 (occasionally up to 22.8) wt % NaCl equiv. The H and O isotopic compositions of sericite from host metasomatic rocks suggest a substantial contribution of seawater to the composition of mineral-forming fluids. The role of magmatic water increases in the central zones of the feeding conduit and with depth. The dual nature of fluids with the prevalence of their magmatic source is supported by S, C, O, and Sr isotopic compositions. The TC parameters of the formation of massive sulfide deposits are consistent with the data on fluid inclusions from contemporary sulfide mounds on the oceanic bottom.     

Chemical composition,volatile components,and trace elements in melts of the Karymskii volcanic center,Kamchatka, and Golovnina volcano,Kunashir Island: Evidence from inclusions in minerals

Melt inclusions were examined in phenocrysts in basalt, andesite, dacite, and rhyodacite from the Karymskii volcanic center in Kamchatka and dacite form Golovnina volcano in Kunashir Island, Kuriles. The inclusions were examined by homogenization and by analyzing glasses in more than 80 inclusions on an electron microscope and ion microprobe. The SiO₂ concentrations in the melt inclusions in plagioclase phenocrysts from basalts from the Karymskii volcanic center vary from 47.4 to 57.1 wt %, these values for inclusions in plagioclase phenocrysts from andesites are 55.7–67.1 wt %, in plagioclase phenocrysts from the dacites and rhyodacites are 65.9–73.1 wt %, and those in quartz in the rhyodacites are 72.2–75.7 wt %. The SiO₂ concentrations in melt inclusions in quartz from dacites from Golovnina volcano range from 70.2 to 77.0 wt %. The basaltic melts are characterized by usual concentrations of major components (wt %): TiO₂ = 0.7–1.3, FeO = 6.8–11.4, MgO = 2.3–6.1, CaO = 6.7–10.8, and K₂O = 0.4–1.7; but these rocks are notably enriched in Na₂O (2.9–7.4 wt % at an average of 5.1 wt %, with the highest Na₂O concentration detected in the most basic melts: SiO₂ = 47.4–52.0 wt %. The concentrations of volatiles in the basic melts are 1.6 wt % for H₂O, 0.14 wt % for S, 0.09 wt % for Cl, and 50 ppm for F. The andesite melts are characterized by high concentrations (wt %) of FeO (6.5 on average), CaO (5.2), and Cl (0.26) at usual concentrations of Na₂O (4.5), K₂O (2.1), and S (0.07). High water concentrations were determined in the dacite and rhyodacite melts: from 0.9 to 7.3 wt % (average of 15 analyses equals 4.5 wt %). The Cl concentration in these melts is 0.15 wt %, and those of F and S are 0.06 and 0.01 wt %, respectively. Melt inclusions in quartz from the dacites of Golovnina volcano are also rich in water: they contain from 5.0 to 6.7 wt % (average 5.6 wt %). The comparison of melt compositions from the Karymskii volcanic center and previously studied melts from Bezymyannyi and Shiveluch volcanoes revealed their significant differences. The former are more basic, are enriched in Ti, Fe, Mg, Ca, Na, and P but significantly depleted in K. The melts of the Karymskii volcanic center are most probably less differentiated than the melts of Bezymyannyi and Shiveluch volcanoes. The concentrations of water and 20 trace elements were measured in the glasses of 22 melt inclusions in plagioclase and quartz from our samples. Unusually high values were obtained for Li concentrations (along with high Na concentrations) in the basaltic melts from the Karymskii volcanic center: from 118 to 1750 ppm, whereas the dacite and rhyolite melts contain 25 ppm Li on average. The rhyolite melts of Golovnina volcano are much poorer in Li: 1.4 ppm on average. The melts of the Karymskii volcanic center are characterized by relative minima at Nb and Ti and maxima at B and K, as is typical of arc magmas.     

Zircon geochemistry and U–Pb age at rare metal deposits of syenite in the Ukrainian Shield

The distribution of rare and rare earth elements in zircon at the Yastrebets, Azov (Zr–REE–Y), and Perzhan (Be) rare metal deposits of the Ukrainian Shield was studied. Additional evidence for magmatic genesis of these deposits is obtained: unaltered zircon is characterized by a magmatic REE distribution spectrum with a somewhat higher δ¹⁸O value than that of the mantle (6.6‰ on average). The final formation stage of the deposit was marked by predominance of fluids enriched in Y, REE, Nb, and heavy oxygen, resulting in anomalous geochemical characteristics of zircon rims and alteration zones (up to 81500 Y ppm, over 10300 ppm Nb, and 13.9‰ δ¹⁸O). The age of zircon formed in ore-bearing Yastrebets and Azov nonnepheline syenite deposits was estimated at ~1770 Ma (U–Pb, SHRIMP-II).     

Magmatogene fluids of metal-bearing reefs in the Bushveld Complex,South Africa: Based on research data on fluid inclusions in quartz

Fluid inclusions in the Merensky Reef quartz and later pegmatite veins crosscutting the Platreef rocks of the Bushveld Complex are studied by a suite of advanced high-precision methods. Based on the conducted studies, we identify a few types of fluids, some having been separated during the crystallization of volatile matter-rich residual melt of original basic magma, while others are derivatives of later felsic (granite) melts that formed crosscutting veins in fully devitrified ultrabasic and basic rocks. The earliest fluid is captured by quartz in symplectitic intergrowths with intercumulus plagioclase from the Merensky Reef pyroxenite occurs as a homogenous dense dry reduced gas (CH₄–N₂ ± CO₂) mixture separated from the aluminosilicate melt at 800–900°C and 3050 bar. The following heterophase highly concentrated fluids (60–80 wt % NaCl eq.) separated at over 550°C and below 3050 bar transport a large number of metals. Major saline components of such fluids included Na, K, Fe, Ca, and Mn chlorides, Ca and Na sulphates and carbonates. According to LA ICP-MS analysis data, inclusions of these fluids contain high concentrations of Fe, Cr, K, and Na at the level of a few wt % and also significant contents of Cu, Sn, Sb, Mo, Au, Ag, Bi, and Ni in a concentration range from a few to thousands of ppm. Relatively lower-temperature (much higher than 450°C) fluids accompanying the crystallization of crosscutting quartz–feldspar pegmatite veins at the Platreef are also highly concentrated (from 70–80% to 40–14 wt % NaCl eq.), oxidized and metal-bearing. High concentrations of metals such as Na, K, Ca, Mn, Fe, and Pb at the level of wt % and also Ni, Co, Cu, As, Mo, Sn, Sb, and Bi (1–500 ppm) in inclusions in quartz of later pegmatite veins suggest the possible participation of magmatogene fluids related to later felsic intrusions in the redistribution of primary magmatic concentrations of metals. The oxidation of reduced heterophase fluids may be the most important geochemical barrier invoking the crystallization of solid mineral phases from heterophase fluids.     

Geochemistry and Zircon U–Pb–Hf Isotopic Systematics of the Sanchahe Quartz Monzonite Intrusion in the North Qinling Tectonic Zone,Central China： Implications for its Petrogenesis and Tectonic Setting

The Sanchahe quartz monzonite intrusion is situated in the middle segment of the North Qinling tectonic belt, Central China mainland, and consists chiefly of sanukitoid–like and granodioritic-monzogranitic rocks. The sanukitoid–like rocks are characterized by quartz monzonites, which display higher Mg#（55.0–59.0）, and enrichments in Na2 O＋K2 O（7.28–8.94 %）, Ni（21-2312 ppm）, Cr（56-4167 ppm）, Sr（553-923 ppm）, Ba（912-1355 ppm） and LREE（（La/Yb）N =9.47–15.3）, from negative to slightly positive Eu anomalies（δEu=＋0.61 to ＋1.10）, but also depletion in Nb, Ta and Ti. The granodioritic-monzogranitic rocks diaplay various Mg#of 6.00-53.0, high Na2 O＋K2 O（7.20– 8.30%）, Sr（455–1081 ppm） and（La/Yb）N（27.6–47.8）, with positive Eu anomalies（δEu=1.03–1.57） and depleted Nb, Ta and Ti. Laser ablation inductively coupled plasma mass spectrometry（LA-ICPMS） zircon U-Pb isotopic dating reveals that the sanukitoid-like rocks were emplaced at two episodes of magmatism at 457±3 Ma and 431±2 Ma, respectively. The monzogranites were emplaced at 445±7Ma. Sanukitoid–like rocks have their εHf（t） values ranging from ＋0.3 to ＋15.1 with Hf–depleted mantle model ages of 445 to 1056 Ma, and the monzogranite shows its εHf（t） values ranging from 21.6 to ＋10.8 with Hf–depleted mantle model ages of 635 to 3183 Ma. Petrological, geochemical and zircon Lu –Hf isotopic features indicate that the magmatic precursor of sanukitoid–like rocks was derived from partial melting of the depleted mantle wedge materials that were metasomatized by fluids and melts related to subduction of oceanic slab, subsequently the sanukitoid magma ascended to crust level. This emplaced mantle magma caused partial melting of crustally metamorphosed sedimentary rocks, and mixing with the crustal magma, and suffered fractional crystallization, which lead to formations of quartz monzonites. However, the magmatic precursor of the granodioritic-monzogranitic rocks were derived from partial melting of subducted oceanic slab basalts. Integrated previous investigation for the adackitic rocks in the south of the intrusion, the Sanchahe intrusion signed that the North Qinling tectonic zone was developed in an early Paleozoic transitionally tectonic background from an island arc to back–arc.     

Amphibole and apatite insights into the evolution and mass balance of Cl and S in magmas associated with porphyry copper deposits

Chlorine and sulfur are of paramount importance for supporting the transport and deposition of ore metals at magmatic–hydrothermal systems such as the Coroccohuayco Fe–Cu–Au porphyry–skarn deposit, Peru. Here, we used recent partitioning models to determine the Cl and S concentration of the melts from the Coroccohuayco magmatic suite using apatite and amphibole chemical analyses. The pre-mineralization gabbrodiorite complex hosts S-poor apatite, while the syn- and post-ore dacitic porphyries host S-rich apatite. Our apatite data on the Coroccohuayco magmatic suite are consistent with an increasing oxygen fugacity (from the gabbrodiorite complex to the porphyries) causing the dominant sulfur species to shift from S^2? to S⁶⁺ at upper crustal pressure where the magmas were emplaced. We suggest that this change in sulfur speciation could have favored S degassing, rather than its sequestration in magmatic sulfides. Using available partitioning models for apatite from the porphyries, pre-degassing S melt concentration was 20–200 ppm. Estimates of absolute magmatic Cl concentrations using amphibole and apatite gave highly contrasting results. Cl melt concentrations obtained from apatite (0.60 wt% for the gabbrodiorite complex; 0.2–0.3 wt% for the porphyries) seems much more reasonable than those obtained from amphibole which are very low (0.37 wt% for the gabbrodiorite complex; 0.10 wt% for the porphyries). In turn, relative variations of the Cl melt concentrations obtained from amphibole during magma cooling are compatible with previous petrological constraints on the Coroccohuayco magmatic suite. This confirms that the gabbrodioritic magma was initially fluid undersaturated upon emplacement, and that magmatic fluid exsolution of the gabbrodiorite and the pluton rooting the porphyry stocks and dikes were emplaced and degassed at 100–200 MPa. Finally, mass balance constraints on S, Cu and Cl were used to estimate the minimum volume of magma required to form the Coroccohuayco deposit. These three estimates are remarkably consistent among each other (ca. 100 km³) and suggest that the Cl melt concentration is at least as critical as that of Cu and S to form an economic mineralization.     

Magmatic Evolution of Changbaishan Tianchi Volcano,China–North Korea: Evidence from Mineral-Hosted Melt and Fluid Inclusions

Data on mineral-hosted melt, fluid, and crystalline inclusions were used to study the composition and evolution of melts that produced rocks of Changbaishan Tianchi volcano, China–North Korea, and estimate their crystallization parameters. The melts crystallized within broad ranges of temperature (1220–700°C) and pressure (3100–1000 bar), at a drastic change in the redox potential: Δ log \(f_{O_2}\) from NNO + 0.92 to +1.42 for the basalt melts, NNO –1.61 to –2.09 for the trachybasaltic andesite melts, NNO –2.63 to –1.89 for the comendite melts, and NNO –1.55 to –3.15 for the pantellerite melts. The paper reports estimates of the compositions of melts that produced the continuous rock series from trachybasalt to comendite and pantellerite. In terms of trace-element concentrations, all of the mafic melts are comparable with OIB magmas. The silicic melts are strongly enriched in trace elements and REE. The most strongly enriched melts contain concentrations of certain elements almost as high as in ores of these elements. The paper reports data on H2O concentrations in melts of different composition. It is demonstrated that the variations in the H₂O concentrations were controlled by magma degassing. Data are reported on the Sr and Nd composition of the rocks. The deviations in the Sr isotopic composition are proportional to the ⁸⁷Sr/⁸⁶Sr ratio and could be produced in a melt with a high enough ⁸⁷Sr/⁸⁶Sr ratio during a geologically fairly brief time period. The evolution of melts that produced rocks of the volcano was controlled by crystallization differentiation of the parental basalt magmas at insignificant involvement of melt mixing and liquid immiscibility of silicate and sulfide melts. The alkaline salic rocks were generated in shallow-sitting (13–3.5 km) magmatic chambers in which the melts underwent profound differentiation that gave rise to pantellerites and comendites strongly enriched in trace elements (Th, Nb, Ta, Zr, and REE). Data on the composition of the magmas and parameters of their derivation are used to develop a generalized petrologic–geodynamic model for the origin of Changbaishan Tianchi volcano.     

Stable isotope evidence for magmatic fluid input during large-scale Na–Ca alteration in the Cloncurry Fe oxide Cu–Au district, NW Queensland, Australia

Sodic–calcic alteration is common in mineralized hydrothermal systems, yet the relative importance of igneous vs. basinal fluid sources remains controversial. One of the most extensive volumes of sodic–calcic rocks occurs near Cloncurry, NW Queensland, and was formed by overlapping hydrothermal systems that were active synchronously with emplacement of mid‐crustal batholithic granitoids (c. 1.55–1.50 Ga). Altered rocks contain albite–oligoclase, actinolite, diopside, titanite and magnetite. Alteration was localized by: (A) composite veins and breccias containing crystallized magma intimately intergrown with hydrothermal precipitates; (B) intrusions that host setting A veins and breccias; and (C) extensive breccia and vein systems linked to regional fault systems. Isotope analyses of actinolites in settings A and B indicate calculated δ¹⁸O_H2O (+8.2 to +10.6‰) and variably depleted δD_H2O (?130 to ?54‰) compared with typical magmatic fluids, whereas those from setting C typically indicate calculated δ¹⁸O_H2O (+8.0 to +12.8‰) and δD_H2O (?29 to ?99‰). The lowest δD_H2O values are interpreted as representing residual fluids after significant (> 90%) open‐system magmatic degassing. Overall the stable isotope, field, geochronological and geobarometric data suggest that these sodic–calcic alteration systems were formed by the episodic incursion of magmatic fluids that underwent minor isotopic modification as a result of varying degrees of interaction with country rocks.     

Calc-alkaline rear-arc magmatism in the Fuegian Andes: Implications for the mid-cretaceous tectonomagmatic evolution of southernmost South America

The magmatic arc of the Fuegian Andes is composed mostly of Upper Mesozoic to Cenozoic calc-alkaline plutons and subordinated lavas. To the rear arc, however, isolated mid-Cretaceous monzonitic plutons and small calc-alkaline dykes and sills crop out. This calc-alkaline unit (the Ushuaia Peninsula Andesites, UPA) includes hornblende-rich, porphyritic quartz meladiorites, granodiorites, andesites, dacites and lamprophyres. Radiometric dating and cross-cutting relationships indicate that UPA is younger than the monzonitic suite. The geochemistry of UPA is medium to high K, with high LILE (Ba 500–2000 ppm, Sr 800–1400 ppm), HFSE (Th 7–23 ppm, Nb 7–13 ppm, Ta 0.5–1.1 ppm) and LREE (La 16–51 ppm) contents, along with relatively low HREE (Yb 1.7–1.3 ppm) and Y (9–19 ppm). The similar mineralogy and geochemistry of all UPA rocks suggest they evolved from a common parental magma, by low pressure crystal fractionation, without significant crustal assimilation. A pure Rayleigh fractionation model indicates that 60–65% of crystal fractionation of 60% hornblende + 34% plagioclase + 4% clinopyroxene + 1% Fe-Ti oxide, apatite and sphene (a paragenesis similar of UPA mafic rocks) can explain evolution from lamprophyres to dacites. The UPA has higher LILE, HFSE and LREE, and lower HREE and Y than the calc-alkaline plutons and lavas of the volcanic front. The HREE and Y are lower than in the potassic plutons as well. High concentrations of Th, Nb, Ta, Zr, Hf, LREE and Ce/Pb, and low U/Th, Ba/Th ratios in UPA, even in the least differentiated samples, suggest contributions from subducted sediments to the mantle source. On the other hand, relatively low HREE and Y, high LREE/HREE (La/Yb 11–38) ratios and Nb-Ta contents can be interpreted as mantle metasomatism by partial melts of either subducted garnetiferous oceanic sediment or basalt as well. Additionally, high LILE content in UPA, similar to the potassic plutons, suggests also a mantle wedge previously metasomatized by potassic parental magmas in their route to crustal levels. Therefore, UPA represents a unique suite in the Fuegian arc generated in a multiple hybridized source. UPA generation is related to a transition from normal to flat subduction which additionally caused the widening and landward migration of the magmatic arc, as well as crustal deformation. Rear-arc magmatism endured ca. 22 m.y.; afterwards, calc-alkaline magmatism remained at the volcanic front.     

Petrogenesis of the Carboniferous Intrusive Rock in the Xiaobaishitou District of East Tianshan, Northwest China: Magma Evolution and Tectonic Significance

The Xiaobaishitou gabbro-diorite pluton comprises a medium-grained gabbro-diorite suite and a fine-grained diorite suite, which intrude the Kawabulag Group in the East Tianshan Orogen of the Central Asian Orogenic Belt(CAOB). A combination of mineral chemistry, zircon U-Pb age, whole-rock geochemistry, Sr-Nd isotopes, and in situ zircon Hf isotopes for newly found gabbro-diorite from the Xiaobaishitou district in the Central Tianshan Terrane(CTT) is presented to investigate the petrogenesis and ...     

The δ18O of UST Quartz in Two Porphyry Deposits,China

The unidirectional solidification textures (UST) quartz is generally thought to form from fluids exsolved from shallow intrusions and/or magma chambers, but such an idea is still poorly constrained from the evidence of stable isotopes. In this study, we report for the first time the δ¹⁸O of quartz that shows UST from the Qulong Cu–Mo and the Yechangping Mo porphyry deposits in China. The analysis results show that the UST quartz samples from the Qulong deposit have δ¹⁸O values ranging from +6.2 ‰ to +7.6 ‰, which are similar to that of quartz phenocrysts (+6.7 ‰ to +7.8 ‰). In contrast, the UST quartz samples from the Yechangping porphyry Mo deposit yield a high δ¹⁸O value (+10.0 ‰). The δ¹⁸O_water value of Yechangping UST quartz (+8.5 ‰) is also higher than that of Qulong (+4.6 ‰ to +5.8 ‰). Hydrothermal biotite from potassic alteration and sericite from early phyllic alteration at Qulong have similar δ¹⁸O values to UST quartz, suggesting the involvement of magmatic fluids during this stage of deposit evolution.     

Lithium isotopic evidence for subduction of the Indian lower crust beneath southern Tibet

Post-collisional K-rich volcanic rocks (KVRs) can provide an opportunity to constrain the architecture of the lithosphere and the mechanisms of plateau uplift. However, their petrogenesis and geodynamic setting remain in dispute. Lithium concentrations and isotopic compositions of 87 potassic, ultrapotassic and Mg-rich potassic volcanic rocks (PVRs, UPVs, and MPRs, respectively) in SW Tibet, along with new Pb–Sr–Nd isotope data and whole-rock analyses, are used to constrain their mantle source and genesis. These rocks are characterized by very similar δ⁷Li values: PVRs vary from −4.9‰ to +3.2‰, UPVs from −3.9‰ to +1.7‰, and MPRs from −1.2‰ to +3.5‰. They can be classified into two groups: Group I (19 out of 87 samples) with heavier δ⁷Li values (+1.0‰ to +3.5‰) similar to those reported for mid-ocean-ridge and ocean-island basalts (MORBs and OIBs, respectively), and Group II (68 out of 87 samples) with lighter values (−4.9‰ to +1.0‰) similar to those of Indian lower crust. These variable isotopic compositions may record the isotopic signature of the early-middle Miocene subcontinental lithospheric mantle (SCLM). This paper demonstrates the existence of isotopically light mantle domains beneath the Lhasa terrane, which were ascribed to the interaction with fluids/melts derived from the subducted Indian lower crust. The modeling curves of Indian lower crust with a metasomatized mantle composition fully account for compositional variations in the PVRs, UPVs, and MPRs. They were generated by the partial melting of SCLM, which was metasomatized by fluids/melts derived from the subducted Indian lower crust (ca. 4–14%, ca. 4–10%, and ca. 6–10% for the PVRs, UPVs, and MPRs, respectively). The Li isotopic data indicate that the Indian lower crust was subducted beneath the central Lhasa subterrane, and this sheds new light on the formation of the Tibet Plateau.     

Geochemical anomalies in the mantle of the Pamirs and Tien Shan with applications to the deep-seated sources of ore material

The mantle metasomatites (fluidized magmatic rocks) of the Pamir-Tien Shan region show extremely high contents of lithophile and chalcophile trace elements, which often exceeds the regional average abundances of the Earth’s crust. Geochemical relations were established between mantle and crustal rocks, and it was shown that the compositions of magmatic rocks of different age and formation depth and polychronous mineralization are relatively stable. These data and some other facts indicate the possible influence of mantle fluids (melts) on the crustal rocks and processes. An alternative model implies the geochemical influence of crustal rocks on the geochemical characteristics of the regional mantle. The ore material of alkali basic rocks and some hydrothermal and rare metal deposits shows a geochemical affinity to the supposed mantle (mantle-crustal) sources. The ore-bearing fluids (melts) were presumably related to the evolution of ultradeep “hot” material of mantle plumes and “daughter” diapirs carrying alkaline, trace, and ore elements.