Boron isotope composition of melt inclusions from porphyry systems of the Central Andes: a reconnaissance study

Quartz-hosted melt inclusions from latite dykes of the Eocene El Salvador copper porphyry system in northern Chile display wide ranges in both boron concentration (15–155 p.p.m. B) and isotope composition (δ¹¹B −7 to +12‰; n  = 10), likely reflecting slab-derived fluid input from seawater-altered oceanic crust. In contrast, the major Miocene tin-silver and tin porphyry systems in the Bolivian back-arc region (Cerro Rico de Potosi, Chorolque, Llallagua) have distinctly different melt inclusion compositions with δ¹¹B of −11.4 ± 2.7‰ ( n  = 10), and magmatic boron enrichment up to several hundred p.p.m. B. The `seawater' signature in the El Salvador melt inclusions explains the oxidized mineral assemblage of the copper porphyry system, as opposed to the more reduced nature of the Bolivian tin porphyry systems, which reflect intracrustal melting of pelitic rocks.     

From rocks to ore

Metal enrichment to ore grade is the ultimate outgrowth of large-scale and long-term fractionation processes of the thermally driven and unique water-cooled geological evolution of the Earth. Silicic magmatism along convergent margins is the most important lithospheric fractionation process for the formation of the continental crust and porphyry/intrusion-related ore deposits. Reconnaissance microanalysis of melt inclusions from Central Andean porphyry systems refines a metallogenic model for copper–gold and tin porphyry mineralization. Magmatic mixing and early exsolution of a fluid phase are important ingredients for porphyry Cu–Au systems in association with silicic rocks of moderate levels of fractionation (such as diorites and monzonites), whereas extended magmatic fractionation with late-stage fluid evolution characterize lithophile-element-enriched tin porphyry systems. Received: 25 June 1999 / Accepted: 11 January 2000     

Depth of emplacement, fluid provenance and metallogeny in granitic terranes: a comparison of western Thailand with other tin belts

The most important tin mineralization in Thailand is associated with the Late Cretaceous to Middle Tertiary western Thai granite belt. A variety of deposit types are present, in particular pegmatite, vein and greisen styles of mineralization. A feature common to most of the deposits is that they are associated with granites that were emplaced into the Khang Krachan Group, which consists of poorly sorted, carbonaceous, pelitic metasediments. Most of the deposits contain low to moderately saline aqueous fluid inclusions and aqueous-carbonic inclusions with variable CH₄/CO₂ ratios. Low salinity aqueous inclusions represent trapped magmatic fluid in at least one case, the Nong Sua pegmatite, based on their occurrence as primary inclusions in magmatic garnet. Aqueous-carbonic inclusions are commonly secondary and neither the CO₂ nor NaCl contents of these inclusions decrease in progressively younger inclusions, implying that they are not magmatic in origin. Reduced carbon is depleted in the metasediments adjacent to granites and the δD values greisen muscovites are variable, but are as low as −134 per mil, indicative of fluid interaction with organic (graphitic) material. This suggests that the aqueous-carbonic fluid inclusions represent fluids that were produced, at least in part, during contact metamorphism-metasomatism. By comparing the western Thai belt with other Sn-W provinces it is evident that there is a strong correlation between fluid composition and pressure in general. Low to moderately saline aqueous inclusions and aqueous-carbonic inclusions are characteristic of mineralization associated with relatively deep plutonic belts. Mineralized pegmatites are also typically of deeper plutonic belts, and pegmatite-hosted deposits may contain cassiterite that is magmatic (crystallized from granitic melt) or is orthomagmatic-hydrothermal (crystallized from aqueous or aqueous-carbonic fluids) in origin. The magmatic aqueous fluids (those that were exsolved from granitic melts) are interpreted to have had low salinities. As a consequence of the low salinities, tin is partitioned in favour of the melt on vapour saturation. Thus with a high enough degree of fractionation, the crystallization of a magmatic cassiterite (or different Sn phase such as wodginite) is inevitable. Because tin is not partitioned in favour of the vapour phase upon water saturation of the granitic melts, it is proposed that relatively deep vein and greisen systems tend to form by remobilization processes. In addition, many deeper greisen systems are hosted, in part, by carbonaceous pelitic metasediments and the reduced nature of the metasediments may play a key role in remobilizing tin. Sub-volcanic systems by contrast are characterized by high temperature-high salinity fluids. Owing to the high chlorinity, tin is strongly partitioned in favour of the vapour and cassiterite mineralization can form by of orthomagmatic-hydrothermal processes. Similar relationships between the depth of emplacement and fluid composition also appear to apply to other types of granite-hosted deposits, such as different types of molybdenum deposits. Received: 8 September 1997 / Accepted: 28 October 1997     

Platinum-group elements in Cu-sulphide ores at Carolusberg and East Okiep, Namaqualand, South Africa

Cu-sulphide ores at Carolusberg and East Okiep have Cu/Ni ratios of up to 80, an order of magnitude higher than most magmatic sulphide ores elsewhere. In contrast, Se/S ratios (500–1700 × 10⁻⁶) and PGE tenors (up to 5 ppm) of the sulphides are in the range of more typical magmatic sulphide ores. The observed metal patterns may be explained by a process of monosulphide solid solution (mss) fractionation of a magmatic sulphide melt at depth, but this model is currently considered unlikely, due to the paucity of refractory ores in the district. Assimilation of Cu-rich country rocks during ascent of the Koperberg magmas proved difficult to test with the available data, but this provides no explanation for the common high-grade metamorphic setting of similar ores elsewhere. A restitic origin of the pyroxenites appears to explain many of the observed ore features and is presently favoured here. Desulphidization of a primary magmatic sulphide ore could not have yielded the observed metal patterns and is therefore considered to be of relatively minor importance in ore genesis. Received: 12 April 1999 / Accepted: 27 November 1999     

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).     

Sulfur isotopic systematics of granitoids from southwestern New Brunswick, Canada: implications for magmatic-hydrothermal processes, redox conditions, and gold mineralization

Bulk δ ³⁴S_rock values, sulfur contents, and magnetic susceptibility were determined for 12 gold-related granitoid intrusions in southwestern New Brunswick, the Canadian Appalachians. The sulfur isotope compositions of sulfide minerals in some of the granitoid samples were also analyzed. This new dataset was used to characterize two distinctive groups of granitoids: (1) a Late Devonian granitic series (GS) and (2) a Late Silurian to Early Devonian granodioritic to monzogranitic series (GMS). The GS rocks have a large range in δ ³⁴S values of −7.1‰ to +13‰ with an average of 2.2 ± 5.0‰ (1σ), low bulk-S contents (33 to 7,710 ppm) and low magnetic susceptibility values (<10⁻⁴ SI), consistent with reduced ilmenite-series granites. The GMS rocks have a relatively narrower variation in δ ³⁴S values of −4.4‰ to +7.3‰ with an average 1.2 ± 2.9‰ but with larger ranges in bulk-S contents (45 to 11,100 ppm) and high magnetic susceptibility values (>10⁻³ SI), indicative of oxidized magnetite-series granites. The exceptions for the GMS rocks are the Lake George granodiorite and Tower Hill granite that display reduced characteristics, which may have resulted from interaction of the magmas forming these intrusions with graphite- or organic carbon-bearing sedimentary rocks. The bulk δ ³⁴S values and S contents of the GMS rocks are interpreted in terms of selective assimilation–fractional crystallization (SAFC) processes. Degassing processes may account for the δ ³⁴S values and S contents of some GS rocks. The characteristics of our sulfur isotope and abundance data suggest that mineralizing components S and Au in intrusion-related gold systems are dominantly derived from magmatic sources, although minor contaminants derived from country rocks are evident. In addition, the molar sulfate to sulfide ratio in a granitic rock sample can be calculated from the δ ³⁴S_rock value of the whole-rock sample and the δ ³⁴S_sulfide (or δ ³⁴S_sulfate) value of sulfide and/or sulfate mineral in the sample on the basis of S-isotope fractionation and mass balance under the condition of magmatic equilibrium. This may be used to predict the speciation of sulfur in granitic rocks, which can be a potential exploration tool for intrusion-related gold systems.     

Boron recycling in the continental crust of the central Andes from the Palaeozoic to Mesozoic, NW Argentina

Whole-rock chemical composition and ¹¹B/¹⁰B isotope ratios in tourmaline was investigated to study the geochemical recycling of boron during the evolution of the Andean basement from the Palaeozoic to Mesozoic. In the basement (Cambrian to Ordovician high-grade paragneisses, migmatites and orthogneisses, the Eocambrian Puncoviscana Formation, and Paleozoic-Mesozoic granitoid igneous rocks) whole-rock B contents are generally below 100 ppm, but B contents of ˜1 wt% are found in cogenetic aplite and pegmatite dikes and in tourmaline–quartz rocks. In the metasedimentary rocks, no systematic variation in B content because of metamorphic grade and no correlation of B with other incompatible elements are apparent. Tourmalines from the high-grade metamorphic basement yield δ¹¹B values ranging from −11.2 to −6.8‰ and isotope fractionation during migmatisation was small. Metamorphic tourmalines from the Puncoviscana Formation have δ¹¹B values between −6.3 and −5.8‰. The calculated (corrected for fractionation) δ¹¹B values of −6 to −2‰ for the sedimentary protolith of the metamorphic basement indicate a continental B source with subordinate marine input. Tourmalines from Palaeozoic and Mesozoic granitoids display an identical range of δ¹¹B values from −12 to −5.3‰ and indicate a similarly homogeneous B source throughout time. Tourmalines from pegmatites and tourmaline–quartz rocks record the average δ¹¹B values of the parental granitic magma. We assume that B in the Palaeozoic and Mesozoic granitoids is derived from the local metamorphic basement supporting the hypothesis that recycling of the lower Palaeozoic crust is the dominant process in granitic magma formation from Palaeozoic to Mesozoic. Received: 15 December 1999 / Accepted: 11 July 2000     

Strong tin enrichment in a pegmatite-forming melt

To investigate processes of magmatic tin enrichment and cassiterite deposition, we studied the abundances of major, trace, and volatile elements in a large number of rehomogenized silicate melt inclusions in quartz and topaz from a pegmatite body at the Ehrenfriedersdorf Sn–W deposit. This deposit is associated with evolved Variscan granites of the central Erzgebirge, southeast Germany. The melt inclusions are peraluminous; the molar aluminum saturation index (ASI) ranges from 1.15 to 2.0, and many inclusions are characterized by a very high content of fluxing components and volatiles. Some inclusions contain more than 20 wt% of H₂O, F, Cl, and P₂O₅, plus Li as well as very high levels of Sn. Some rare, highly evolved fractions of late-stage pegmatite-forming liquid at Ehrenfriedersdorf contained up to 7000 ppm Sn. The presence of hydrogen and methane in addition to water and carbon dioxide in the vapor phase of the melt inclusions suggests a very low oxygen fugacity for some fractions of magma. The extreme levels of tin, volatiles, and fluxing components in this magma had an important influence on processes of melt movement and cassiterite precipitation. Melts, like these, that are high in volatiles and alkalis (sum of Li₂O, Na₂O, K₂O, Rb₂O, and Cs₂O is >8 wt%) have low densities (≤1.8 g/cm³), low viscosities (<10 Pa.s at 700 °C), facilitate relatively rapid diffusion of ions through melts, and hence are excellent solvents for extracting and transporting ore-forming elements. Received: 1 February 1999 / Accepted: 19 January 2000     

Boron in granitic magmas: stability of tourmaline in equilibrium with biotite and cordierite

Experiments at 750 °C, 200 MPa_(H2O), a _(H2O)=1, and fO₂∼Ni-NiO established that the equilibrium among tourmaline, biotite, cordierite, and melt (± spinel, aluminosilicate, or corundum) occurs with ∼2 wt% B₂O₃ in strongly peraluminous melt with an aluminosity, measured by the parameter ASI, of >1.2. The experiments demonstrate the relationship of tourmaline stability to the activity product of the tourmaline components boron and aluminum, which are inversely related to one another. Tourmaline is unstable in metaluminous to mildly peraluminous melts (ASI <1.2) at 750 °C regardless of their boron content. For a given aluminosity, addition of components such as F requires a greater boron content of melt at this equilibrium. The stability of tourmaline increases with decreasing temperatures below 750 °C. At the inception of melting, tourmaline breaks down incongruently to assemblages containing crystalline AFM silicates (biotite, cordierite, garnet, sillimanite), aluminates (spinel, corundum), and B-enriched but Fe-Mg-poor melt. Granitic melts are likely to be undersaturated in tourmaline from the start of their crystallization, and their initial boron contents will be limited by the abundance of tourmaline in their source rocks. Quartzofeldspathic (gneissic, metapelitic) rocks that reached conditions of the granulite facies and still contain (prograde) tourmaline are rare, and probably have never yielded a partial melt. Most leucogranitic magmas will initially crystallize biotite, cordierite, or garnet, but not tourmaline. With crystallization, the Fe-Mg content of melt decreases, and the B₂O₃ content increases until the tourmaline-biotite and/or tourmaline-cordierite (or garnet) equilibria are attained. The B₂O₃ content of melt is buffered as long as these equilibria continue to operate, but low initial Fe-Mg contents of the magmas limit the quantity of boron that can be consumed by these reactions to <1 wt% B₂O₃. Normally, leucogranitic magmas contain insufficient Fe and Mg to conserve all boron as tourmaline and thus lose a large fraction of magmatic boron to wallrocks. Leucogranites and pegmatites with tourmaline as an early and only AFM silicate mineral probably contained >2 wt% B₂O₃ in their bulk magmas. Received: 6 August 1996 / Accepted: 21 July 1997     

Melt inclusions in pegmatite quartz: complete miscibility between silicate melts and hydrous fluids at low pressure

Fluorine-, boron- and phosphorus-rich pegmatites of the Variscan Ehrenfriedersdorf complex crystallized over a temperature range from about 700 to 500 °C at a pressure of about 1 kbar. Pegmatite quartz crystals continuously trapped two different types of melt inclusions during cooling and growth: a silicate-rich H₂O-poor melt and a silicate-poor H₂O-rich melt. Both melts were simultaneously trapped on the solvus boundaries of the silicate (+ fluorine + boron + phosphorus) − water system. The partially crystallized melt inclusions were rehomogenized at 1 kbar between 500 and 712 °C in steps of 50 °C by conventional rapid-quench hydrothermal experiments. Glasses of completely rehomogenized inclusions were analyzed for H₂O by Raman spectroscopy, and for major and some trace elements by EMP (electron microprobe). Both types of melt inclusions define a solvus boundary in an X_H2O–T pseudobinary system. At 500 °C, the silicate-rich melt contains about 2.5 wt% H₂O, and the conjugate water-rich melt about 47 wt% H₂O. The solvus closes rapidly with increasing temperature. At 650 °C, the water contents are about 10 and 32 wt%, respectively. Complete miscibility is attained at the critical point: 712 °C and 21.5 wt% H₂O. Many pegmatites show high concentrations of F, B, and P, this is particularly true for those pegmatites associated with highly evolved peraluminous granites. The presence of these elements dramatically reduces the critical pressure for fluid–melt systems. At shallow intrusion levels, at T ≥ 720 °C, water is infinitely soluble in a F-, B-, and P-rich melt. Simple cooling induces a separation into two coexisting melts, accompanied with strong element fractionation. On the water-rich side of the solvus, very volatile-rich melts are produced that have vastly different physical properties as compared to “normal” silicate melts. The density, viscosity, diffusivity, and mobility of such hyper-aqueous melts under these conditions are more comparable to an aqueous fluid. Received: 15 September 1999 / Accepted: 10 December 1999     

Chemical composition,volatile components,and trace elements in the magmatic melt of the Kurama mining district,Middle Tien Shan: Evidence from the investigation of inclusions in quartz

Melt and fluid inclusions were investigated in six quartz phenocryst samples from the igneous rocks of the extrusive (ignimbrites and rhyolites) and subvolcanic (granite porphyries) facies of the Lashkerek Depression in the Kurama mining district, Middle Tien Shan. The method of inclusion homogenization was used, and glasses from more than 40 inclusions were analyzed on electron and ion microprobes. The chemical characteristics of these inclusions are typical of silicic magmatic melts. The average composition is the following (wt %): 72.4 SiO₂, 0.06 TiO₂, 13.3 Al₂O₃, 0.95 FeO, 0.03 MnO, 0.01 MgO, 0.46 CaO, 3.33 Na₂O, 5.16K₂O, 0.32 F, and 0.21 Cl. Potassium strongly prevails over sodium in all of the inclusions (K₂O/Na₂O averages 1.60). The average total of components in melt inclusions from five samples is 95.3 wt %, which indicates a possible average water content in the melt of no less than 3–4 wt %. Water contents of 2.0 wt % and 6.6 wt % were determined in melt inclusions from two samples using an ion microprobe. The analyses of ore elements in the melt inclusions revealed high contents of Sn (up to 970 ppm), Th (19–62 ppm, 47 ppm on average), and U (9–26 ppm, 18 ppm on average), but very low Eu contents (0.01 ppm). Melt inclusions of two different compositions were detected in quartz from a granite porphyry sample: silicate and chloride, the latter being more abundant. In addition to Na and K chlorides, the salt inclusions usually contain one or several anisotropic crystals and an opaque phase. The homogenization temperatures of the salt inclusions are rather high, from 680 to 820°C. In addition to silicate inclusions with homogenization temperatures of 820–850°C, a primary fluid inclusion of aqueous solution with a concentration of 3.7 wt % NaCl eq. and a very high density of 0.93 g/cm³ was found in quartz from the ignimbrite. High fluid pressure values of 6.5–8.3 kbar were calculated for the temperature of quartz formation. These estimates are comparable with values obtained by us previously for other regions of the world: 2.6–4.3 kbar for Italy, 3.7 kbar for Mongolia, 3.3–8.7 kbar for central Slovakia, and 3.3–9.6 kbar for eastern Slovakia. Unusual melt inclusions were investigated in quartz from another ignimbrite sample. In addition to a gas phase and transparent glass, they contain spherical Feoxide globules (81.2 wt % FeO) with high content of SiO₂ (9.9 wt %). The globules were dissolved in the silicate melt within a narrow temperature range of 1050–1100°C, and the complete homogenization of the inclusions was observed at temperatures of 1140°C or higher. The combined analysis of the results of the investigation of these inclusions allowed us to conclude that immiscible liquids were formed in the high-temperature silicic magma with the separation of iron oxide-dominated droplets.     

江西会昌锡坑迳斑岩型锡矿床成矿系统发育特征与找矿模型

锡坑迳矿田位于南岭成矿带东段与武夷山成矿带交会部位,以早白垩世连续的岩浆喷发-侵入活动与多类型锡多金属成矿作用为特色。矿田内围绕似斑状花岗岩和花岗斑岩发育了岩背斑岩型、淘锡坝和矿背隐爆层间裂隙带型、苦竹岽和凤凰岽云英岩-破碎带蚀变岩型等大中型锡矿床。这些矿床的矿化-蚀变特征可与玻利维亚锡矿带、银岩、维拉斯托和洋滨等国内外斑岩型锡矿床类比,又独具特色,是研究斑岩型锡成矿系统发育特征与找矿模型的理想区域。文章在详细的野外地质调查基础上,系统总结了锡坑迳矿田内各类锡多金属矿化组合特征和蚀变结构,并对岩背矿床和淘锡坝矿床锡石开展了电子探针和LA-ICP-MS原位微区分析。研究结果显示,所有锡石样品均具有La、Pr、Gd和Tb的正异常、Ce与Eu的负异常、明显的Zr/Hf分馏和不规则的稀土元素配分模式,指示成矿热液早期阶段及锡石沉淀阶段经历了流体不相容。岩背锡石较淘锡坝锡石具有高的Ti/Zr和Ti/Sc比值,指示其更为靠近矿化中心。笔者研究认为,锡坑迳斑岩型锡成矿系统矿化类型包括细脉状、浸染状和细网脉状,围岩蚀变由早到晚、由成矿中心向外依次发育黄玉石英带、绿泥石-黄玉石英岩化带、绿泥石-绢云母化带和黏土化-碳酸盐化带。与斑岩型铜钼成矿系统相比,其成矿岩浆岩不仅有花岗斑岩,还有似斑状黑云母花岗岩,矿体在斑岩、花岗岩及上覆火山岩中均有赋存。相较于玻利维亚斑岩型锡成矿带发育的大面积石英-电气石化,锡坑迳斑岩成矿系统更富F,蚀变矿物中出现了大量黄玉、萤石和白云母等。对比国内外典型锡矿床的矿化-蚀变结构和锡石矿物学特征,文章建立了锡坑迳式斑岩型锡成矿系统的找矿模型。     

General characteristics of the geochemical evolution of silicic melts during the development of massive sulfide magmatic ore systems: Evidence from the investigation of melt inclusions

The investigation of melt inclusions in the minerals of volcanic rocks from the massive sulfide deposits of Siberia and the Urals revealed some specific features in the development of their magmatic ore systems. It was shown that the petrochemical and rare earth element compositions of melt inclusions reflect the geodynamic conditions of their formation: island arc conditions for the massive sulfide deposits of Rudny Altai, eastern Tuva, and the Salair Range and a back arc basin environment for the Yaman-Kasy deposit. The silicic melts of inclusions from the volcanic rocks of massive sulfide deposits show some specific features with respect to the contents of volatile components. In all of the ore deposits studied, fluorine content was always low (0.03–0.08 wt %), whereas chlorine content (0.13–0.28 wt %) was higher than the average value for silicic melts (0.17 wt %). There is a strong differentiation of water content in melt inclusions, both between deposits and between various volcanics from a single deposit. Ore-bearing melts show the highest water contents of 3.34–4.07 wt %. High Cu contents in the silicic melts of the Yubileinoe and Kyzyl-Tashtyg deposits (up to 7118 and 3228 ppm, respectively) may indicate the affinity of some ore components to particular silicic magmas. This is supported by the elevated contents of Cu in the porphyry Cu deposits of Romania (Valea Morii), Mongolia (Bayan Ula), and Bolivia. On the other hand, the silicic melts of inclusions from the molybdenum-uranium deposit of the Strel’tsovka ore field show high contents of another group of ore components (U and F).     

Geology and vein tin mineralization in the Dadoushan deposit,Gejiu district,SW China

Vein-type tin mineralization in the Dadoushan deposit, Laochang ore field, Gejiu district, SW China, is predominantly hosted in Triassic carbonate rocks (Gejiu Formation) over cupolas of the unexposed Laochang equigranular granite intrusion. The most common vein mineral is tourmaline, accompanied by skarn minerals (garnet, diopside, epidote, phlogopite) and beryl. The main ore mineral is cassiterite, accompanied by minor chalcopyrite, pyrrhotite, and pyrite, as well as scheelite. The tin ore grade varies with depth, with the highest grades (~1.2 % Sn) prevalent in the lower part of the vein zone. Muscovite ⁴⁰Ar–³⁹Ar dating yielded a plateau age of 82.7 ± 0.7 Ma which defines the age of the vein-type mineralization. Measured sulfur isotope compositions (δ ³⁴S = −4.1 to 3.9 ‰) of the sulfides (arsenopyrite, chalcopyrite, pyrite, and pyrrhotite) indicate that the sulfur in veins is mainly derived from a magmatic source. The sulfur isotope values of the ores are consistent with those from the underlying granite (Laochang equigranular granite, −3.7 to 0.1 ‰) but are different from the carbonate wall rocks of the Gejiu Formation (7.1 to 11.1 ‰). The calculated and measured oxygen and hydrogen isotope compositions of the ore-forming fluids (δ ¹⁸O_H2O = −2.4 to 5.5 ‰, δD = −86 to −77 ‰) suggest an initially magmatic fluid which gradually evolved towards meteoric water during tin mineralization.     

Garnet-bearing tonalitic porphyry from East Kunlun,Northeast Tibetan Plateau: implications for adakite and magmas from the MASH Zone

A garnet-bearing tonalitic porphyry from the Achiq Kol area, northeast Tibetan Plateau has been dated by SHRIMP U-Pb zircon techniques and gives a Late Triassic age of 213 ± 3 Ma. The porphyry contains phenocrysts of Ca-rich, Mn-poor garnet (CaO > 5 wt%; MnO < 3 wt%), Al-rich hornblende (Al₂O₃ ~ 15.9 wt%), plagioclase and quartz, and pressure estimates for hornblende enclosing the garnet phenocrysts yield values of 8–10 kbar, indicating a minimum pressure for the garnet. The rock has SiO₂ of 60–63 wt%, low MgO (<2.0 wt%), K₂O (<1.3 wt%), but high Al₂O₃ (>17 wt%) contents, and is metaluminous to slightly peraluminous (ACNK = 0.89–1.05). The rock samples are enriched in LILE and LREE but depleted in Nb and Ti, showing typical features of subduction-related magmas. The relatively high Sr/Y (~38) ratios and low HREE (Yb < 0.8 ppm) contents suggest that garnet is a residual phase, while suppressed crystallization of plagioclase and lack of negative Eu anomalies indicate a high water fugacity in the magma. Nd–Sr isotope compositions of the rock (εNd_T = −1.38 to −2.33; ⁸⁷Sr/⁸⁶Sr_i = 0.7065–0.7067) suggest that both mantle- and crust-derived materials were involved in the petrogenesis, which is consistent with the reverse compositional zoning of plagioclase, interpreted to indicate magma mixing. Both garnet phenocrysts and their ilmenite inclusions contain low MgO contents which, in combination with the oxygen isotope composition of garnet separates (+6.23‰), suggests that these minerals formed in a lower crust-derived felsic melt probably in the MASH zone. Although the rock samples are similar to adakitic rocks in many aspects, their moderate Sr contents (<260 ppm) and La/Yb ratios (mostly 16–21) are significantly lower than those of adakitic rocks. Because of high partition coefficients for Sr and LREE, fractionation of apatite at an early stage in the evolution of the magma may have effectively decreased both Sr and LREE in the residual melt. It is suggested that extensive crystallization of apatite as an early phase may prevent some arc magmas from evolving into adakitic rocks even under high water fugacity.     

Columbite solubility in granitic melts: consequences for the enrichment and fractionation of Nb and Ta in the Earth's crust

The behaviour of niobium and tantalum in magmatic processes has been investigated by conducting MnNb₂O₆ and MnTa₂O₆ solubility experiments in nominally dry to water-saturated peralkaline (aluminium saturation index, A.S.I. 0.64) to peraluminous (A.S.I. 1.22) granitic melts at 800 to 1035 °C and 800 to 5000 bars. The attainment of equilibrium is demonstrated by the concurrence of the solubility products from dissolution, crystallization, Mn-doped and Nb- or Ta-doped experiments at the same pressure and temperature. The solubility products of MnNb₂O₆ (K_sp ^Nb) and MnTa₂O₆ (K_sp ^Ta) at 800 °C and 2 kbar both increase dramatically with alkali contents in water-saturated peralkaline melts. They range from 1.2 × 10⁻⁴ and 2.6 × 10⁻⁴ mol²/kg², respectively, in subaluminous melt (A.S.I. 1.02) to 202 × 10⁻⁴ and 255 × 10⁻⁴ mol²/kg², respectively, in peralkaline melt (A.S.I. 0.64). This increase from the subaluminous composition can be explained by five non-bridging oxygens being required for each excess atom of Nb⁵⁺ or Ta⁵⁺ that is dissolved into the melt. The K_sp ^Nb and K_sp ^Ta also increase weakly with Al content in peraluminous melts, ranging up to 1.7 × 10⁻⁴ and 4.6 × 10⁻⁴ mol²/kg², respectively, in the A.S.I. 1.22 composition. Columbite-tantalite solubilities in subaluminous and peraluminous melts (A.S.I. 1.02 and 1.22) are strongly temperature dependent, increasing by a factor of 10 to 20 from 800 to 1035 °C. By contrast columbite-tantalite solubility in the peralkaline composition (A.S.I. 0.64) is only weakly temperature dependent, increasing by a factor of less than 3 over the same temperature range. Similarly, K_sp ^Nb and K_sp ^Ta increase by more than two orders of magnitude with the first 3 wt% H₂O added to the A.S.I. 1.02 and 1.22 compositions, whereas there is no detectable change in solubility for the A.S.I. 0.64 composition over the same range of water contents. Solubilities are only slightly dependent on pressure over the range 800 to 5000 bars. The data for water-saturated sub- and peraluminous granites have been extrapolated to 600 °C, conditions at which pegmatites and highly evolved granites may crystallize. Using a melt concentration of 0.05 wt% MnO, 70 to 100 ppm Nb or 500 to 1400 ppm Ta are required for manganocolumbite and manganotantalite saturation, respectively. The solubility data are also used to model the fractionation of Nb and Ta between rutile and silicate melts. Predicted rutile/melt partition coefficients increase by about two orders of magnitude from peralkaline to peraluminous granitic compositions. It is demonstrated that the γNb₂O₅/γTa₂O₅ activity coefficient ratio in the melt phase depends on melt composition. This ratio is estimated to decrease by a factor of 4 to 5 from andesitic to peraluminous granitic melt compositions. Accordingly, all the relevant accessory phases in subaluminous to peraluminous granites are predicted to incorporate Nb preferentially over Ta. This explains the enrichment of Ta over Nb observed in highly fractionated granitic rocks, and in the continental crust in general. Received: 9 August 1996 / Accepted: 26 February 1997     

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.     

Geochemistry and isotope systematics of calc-alkaline volcanic rocks from the Saar-Nahe basin (SW Germany) – implications for Late-Variscan orogenic development

Late Carboniferous (300–290 Ma) calc-alkaline basalts, andesites, and rhyolites typical of volcanic arc settings occur in the intermontane Saar-Nahe basin (SW Germany) within the Variscan orogenic belt. The volcanic rock suite was emplaced under a regime of tensional tectonics during orogenic collapse and its origin has been explained by melting of mantle and crust in the course of limited lithospheric rifting. We report major, trace and rare-earth-element data (REE), and Nd-Pb-Sr-O isotope ratios for a representative sample suite, which are fully consistent with an origin closely related to plate subduction. Major and trace element data define continuous melt differentiation trends from a precursor basaltic magma involving fractional crystallization of olivine, pyroxene, plagioclase, and magnetite typical of magma evolution in a volcanic arc. This finding precludes an origin of the andesitic compositions by mixing of mafic and felsic melts as can be expected in anorogenic settings. The mafic samples have high Mg numbers (Mg# = 65–73), and high Cr (up to 330 ppm) and Ni (up to 200 ppm) contents indicating derivation from a primitive parental melt that was formed in equilibrium with mantle peridotite. We interpret the geochemical characteristics of the near-primary basalts as reflecting their mantle source. The volcanic rocks are characterized by enrichment in the large ion lithophile elements (LILE), negative Nb and Ti, and positive Pb anomalies relative to the neighboring REE, suggesting melting of a subduction-modified mantle. Initial _Nd values of −0.7 to −4.6, Pb, and ⁸⁷Sr/⁸⁶Sr_(t) isotope ratios for mafic and felsic volcanics are similar and indicate partial melting of an isotopically heterogeneous and enriched mantle reservoir. The enrichment in incompatible trace elements and radiogenic isotopes of a precursor depleted mantle may be attributed to addition of an old sedimentary component. The geochemical characteristics of the Saar-Nahe volcanic rocks are distinct from typical post-collisional rock suites and they may be interpreted as geochemical evidence for ongoing plate subduction at the margin of the Variscan orogenic belt not obvious from the regional geologic context. Received: 3 August 1998 / Accepted: 2 January 1999     

The boron isotope geochemistry of tourmaline-rich alteration in the IOCG systems of northern Chile: implications for a magmatic-hydrothermal origin

Hydrothermal tourmaline is common in the iron oxide-copper-gold (IOCG) deposits of the Coastal Cordillera of Chile where it occurs as large crystals in the groundmass of magmatic-hydrothermal breccias, such as in the Silvita or Tropezón ore bodies, or as small grains in replacive bodies or breccia cement in the ore-bearing andesite, as seen at the Candelaria or Carola deposits. Tourmaline shows strong chemical zoning and has a composition of schorl–dravite with significant povondraite and uvite components. The observed boron isotope composition is fairly variable, between −10.4‰ and +6.0‰ with no major differences among the different deposits, suggesting a common genetic mechanism. The δ¹¹B values are significantly lower than those of seawater or marine evaporites and very similar to those of younger porphyry copper deposits and volcanic rocks in the region, indicating that the boron has a common, likely magmatic, origin. The predominant boron source was ultimately dewatering of the subducting slab with a significant contribution derived from the overlying continental basement. The range of δ¹¹B values is between those of the porphyry copper deposits and the porphyry tin deposits of the Andes, suggesting that the IOCG mineralization might be genetically related to fluids having more crustal contamination than the porphyry copper deposits; such an interpretation is at odds with current models that propose that the Andean IOCG deposits are related to juvenile melts or to the circulation of basinal brines. Furthermore, the obtained δ¹¹B data are markedly different from those of the tourmaline in the Carajás IOCG district (Brazil), suggesting that IOCGs do not form by a unique mechanism involving only one type of fluids.     

Rock—Forming and Ore—Forming Temperatures of Lianhuashan Tungsten Deposit,Guangdong Province

The Lianhuashan tungsten deposit occurs in the volcanic terrain in the coastal area of Southeast China,where rhyolite,quartz porphyry and granite consitute a complee magmatic series.The orebodies are located in the endo-and exo-contacts between the quartz porphyry and the metasandstone of the Xiaoping coal measues.Hongenization temperatures of melt inclusions in zircon and quartz are 1100℃and 1050℃ for rhyolite,1000℃ and 860℃for quartz porphyry,and 950-1000℃and 820℃ for granite,respectively,demonstrating that the rockforming temperatures dropped successively from the eruptive to the intrusive rocks and that the homogenization temperatures of melt inclusions in zircon are 50-180℃higher than those in quartz.Homogenization temperatures of gas-liquid inclusions in quartz are 230-520℃（mostly 230-270℃）for quartz porphyry,200-450℃（mostly 200-360℃）for ore-bearing quartz veins,150-210℃for granite 170-200℃ for the vein quartz in it.Quartz from the quartz porphyry and from the ore-earing quartz veins show similar characteristics in inclusion type and homogenization temperature,indicating that intergranular solutions must have been formed upon cooling of magma and that ore-forming solutions for the tungstem mineralization were evolved mainly from ore-bearing intergranular solutions in the quartz porphyry.