Petrographic and geochemical arguments for hydrothermal formation of the Ouenza siderite deposit (NE Algeria)

The Ouenza siderite deposit is located proximal to evaporitic diapirs of Triassic age. Mineralization occurs mainly in Aptian neritic limestones which host important iron concentrations (120–150 MT) and minor Pb, Zn, Cu, Ba and F occurrences. The iron ore consists of iron carbonate minerals which have been oxidized partially to hematite. Fine-grained ankerite and siderite replace limestones, whereas sparry ankerite and siderite were emplaced in veins. Limited variation in the chemical and isotopic compositions of ankerite and siderite were observed, which indicate that they precipitated from the same fluid. Stable isotope compositions (δ¹⁸O and δ¹³C) of iron carbonates and limestones allow estimation of the isotopic composition of the mineralizing fluid and precipitation temperature: δ¹⁸O = 7.5‰ SMOW, T = 100–120 °C. Later deposition of Pb, Zn, Cu, Ba and F minerals is controlled by fractures oriented NE–SW and SE–NW. Fluid inclusion studies of quartz yield salinities of 18–22 wt.% equivalent NaCl and homogenization temperatures between 150 and 180 °C. These values are similar to those of Mississippi Valley type deposits which are associated with basinal brines. Received: 4 January 1996 / Accepted: 17 July 1996     

Variation of Mo isotopes from molybdenite in high-temperature hydrothermal ore deposits

Measurable molybdenum isotope fractionation in molybdenites from different ore deposits through time provides insights into ore genesis and a new technique to identify open-system behavior of Re–Os in molybdenites. Molybdenite samples from six porphyry copper deposits, one epithermal polymetallic vein deposit, four skarns, and three Fe-oxide Cu–Au deposits were analyzed. The δ⁹⁷Mo‰ (where ) for all samples varied from 1.34 ± 0.09‰ to −0.26 ± 0.04‰. This is the largest molybdenum isotopic variation in molybdenite from high-temperature ore deposits recorded to date. δ⁹⁷Mo‰ of molybdenite varies as a function of the deposit type and the rhenium and osmium concentrations of the samples. Isotope values for Mo also vary within the individual deposits. In general, molybdenites from porphyry copper deposits have the lightest values averaging 0.07 ± 0.23‰ (1σ). Molybdenites from the other deposit types average 0.49 ± 0.26‰ (1σ). The variations could be related to the fractionation of Mo into different mineral phases during the ore-forming processes. A comparison of the Mo isotope ratios and the Re–Os ages obtained from the same aliquot may possess a geochronological evaluation tool. Samples that yielded robust ages have different Mo isotopic compositions in comparison to samples that yielded geologically unreasonable ages. Another observed relationship between the Re–Os and Mo isotope data reveals a weak correspondence between Re concentration and Mo isotope composition. Molybdenites with higher concentrations of Re correspond to lighter Mo isotope values.     

Time relationships between volcanism–plutonism–alteration–mineralization in Cu-stratabound ore deposits from the Michilla mining district,northern Chile: a <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar geochronological approach

The Michilla mining district comprises one of the most important stratabound and breccia-style copper deposits of the Coastal Cordillera of northern Chile, hosted by the Middle Jurassic volcanic rocks of the La Negra Formation. ⁴⁰Ar/³⁹Ar analyses carried out on igneous and alteration minerals from volcanic and plutonic rocks in the district allow a chronological sequence of several magmatic and alteration events of the district to be established. The first event was the extrusion of a thick lava series of the La Negra Formation, dated at 159.9 ± 1.0 Ma (2σ) from the upper part of the series. A contemporaneous intrusion is dated at 159.6 ± 1.1 Ma, and later intrusive events are dated at 145.5 ± 2.8 and 137.4 ± 1.1 Ma, respectively. Analyzed alteration minerals such as adularia, sericite, and actinolite apparently give valid ⁴⁰Ar/³⁹Ar plateau and miniplateau ages. They indicate the occurrence of several alteration events at ca. 160–163, 154–157, 143–148, and 135–137 Ma. The first alteration event, being partly contemporaneous with volcanic and plutonic rocks, was probably produced in a high thermal gradient environment. The later events may be related either to a regional low-grade hydrothermal alteration/metamorphism process or to plutonic intrusions. The Cu mineralization of the Michilla district is robustly bracketed between 163.6 ± 1.9 and 137.4 ± 1.1 Ma, corresponding to dating of actinolite coexisting with early-stage chalcocite and a postmineralization barren dyke, respectively. More precisely, the association of small intrusives (a dated stock from the Michilla district) with Cu mineralization in the region strongly suggests that the main Michilla ore deposit is related to a magmatic/hydrothermal event that occurred between 157.4 ± 3.6 and 163.5 ± 1.9 Ma, contemporaneous or shortly after the extrusion of the volcanic sequence. This age is in agreement with the Re–Os age of 159 ± 16 Ma obtained from the mineralization itself (Tristá-Aguilera et al., Miner Depos, 41:99–105,2006).     

Oxygen isotope systematics of emerald: relevance for its origin and geological significance

Oxygen isotopic composition of emerald from 62 occurrences and deposits in the world reveals a wide range in δ¹⁸O (SMOW) between +6.2 and +24.7‰. The δ¹⁸O-values for each deposit are restricted and can be used to determine the origin of emerald from the world's most important producers. The δ¹⁸O-value of emerald appears to be a fingerprint of its origin, especially for gems of exceptional quality from Colombia (eastern emerald zone, δ¹⁸O = +16.8 ± 0.1‰; western emerald zone, δ¹⁸O = +21.2 ± 0.5‰), Afghanistan (δ¹⁸O = +13.5 ± 0.1‰), Pakistan (Swat-Mingora districts, δ¹⁸O = +15.7 ± 0.1‰), Brazil (Santa Terezinha de Goiás, δ¹⁸O = +12.2 ± 0.1‰; Quadrilatero Ferrifero, δ¹⁸O = +6.9 ± 0.4‰) and Zimbabwe (Sandawana, δ¹⁸O = +7.5 ± 0.5‰). Furthermore, the ¹⁸O-composition of emerald appears to be a good marker of its geological environment because the data suggest that host-rock-buffering of fluid δ¹⁸O is considerable during fluid-rock interaction. Received: 29 January 1998 / Accepted: 25 March 1998     

Sulfur isotope characteristics of the Archean Cu–Zn Gossan Hill VHMS deposit, Western Australia

Gossan Hill is an Archean (∼3.0 Ga) Cu–Zn–magnetite-rich volcanic-hosted massive sulfide (VHMS) deposit in the Yilgarn Craton of Western Australia. Massive sulfide and magnetite occur within a layered succession of tuffaceous, felsic volcaniclastic rocks of the Golden Grove Formation. The Gossan Hill deposit consists of two stratigraphically separate ore zones that are stratabound and interconnected by sulfide veins. Thickly developed massive sulfide and stockwork zones in the north of the deposit are interpreted to represent a feeder zone. The deposit is broadly zoned from a Cu–Fe-rich lower ore zone, upwards through Cu–Zn to Zn–Ag–Au–Pb enrichment in the upper ore zone. New sulfur isotope studies at the Gossan Hill deposit indicate that the variation is wider than previously reported, with sulfide δ³⁴S values varying between −1.6 and 7.8‰ with an average of 2.1 ± 1.4‰ (1σ error). Sulfur isotope values have a broad systematic stratigraphic increase of approximately 1.2‰ from the base to the top of the deposit. This variation in sulfur isotope values is significant in view of typical narrow ranges for Archean VHMS deposits. Copper-rich sulfides in the lower ore zone have a narrower range (δ³⁴S values of −1.6 to 3.4‰, average ∼1.6 ± 0.9‰) than sulfides in the upper ore zone. The lower ore zone is interpreted to have formed from a relatively uniform reduced sulfur source dominated by leached igneous rock sulfur and minor magmatic sulfur. Towards the upper Zn-rich ore zone, an overall increase in δ³⁴S values is accompanied by a wider range of δ³⁴S values, with the greatest variation occurring in massive pyrite at the southern margin of the upper ore zone (−1.0 to 7.8‰). The higher average δ³⁴S values (2.8 ± 2.1‰) and their wider range are explained by mixing of hydrothermal fluids containing leached igneous rock sulfur with Archean seawater (δ³⁴S values of 2 to 3‰) near the paleoseafloor. The widest range of δ³⁴S values at the southern margin of the deposit occurs away from the feeder zone and is attributed to greater seawater mixing away from the central upflow zone. Received: 10 June 1999 / Accepted: 28 December 1999     

Sulfur and lead isotope geochemistry of hypogene mineralization at the Barite Hill Gold Deposit, Carolina Slate Belt, southeastern United States: a window into and through regional metamorphism

The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110 metric tons of gold over the past 10 years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite–barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The δ³⁴S values of massive barite cluster tightly between 25.0 and 28.0‰, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The δ³⁴S values of massive sulfide range from 1.0 to 5.3‰ and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, δ³⁴S values for finer-grained, intergrown pyrite (5.1–6.8‰) and barite (21.0–23.9‰) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite–pyrite pairs (Δ=15.9–17.1‰) range from 332–355 °C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for ²⁰⁶Pb/²⁰⁴Pb from 18.005–18.294, for ²⁰⁷Pb/²⁰⁴Pb from 15.567–15.645, and for ²⁰⁸Pb/²⁰⁴Pb from 37.555–38.015. The data indicate derivation of the ore leads from the country rocks, which themselves show evidence for contributions from relatively unradiogenic, mantle-like lead, and more evolved or crustal lead. Geological relationships, and stable and radiogenic isotopic data, suggest that the Barite Hill gold deposit formed on the Late Proterozoic seafloor through exhalative hydrothermal processes similar to those that were responsible for the massive sulfide deposits of the Kuroko district, Japan. On the basis of similarities with other gold-rich massive sulfide deposits and modern seafloor hydrothermal systems, the gold at Barite Hill was probably introduced as an integral part of the formation of the massive sulfide deposit. Received: 17 August 1998 / Accepted: 12 October 2000     

Sulfur isotope characteristics of metamorphosed Zn–Cu volcanogenic massive sulfides in the Areachap Group, Northern Cape Province, South Africa

Zn- and Cu-rich massive sulfide ores of volcanogenic origin [volcanogenic massive sulfide (VMS) deposits] occur as stratiform/stratabound lenses of variable size hosted by gneisses, amphibolites, and schists of the Areachap Group, in the Northern Cape Province of South Africa. The Areachap Group represents the highly deformed and metamorphosed remnants of a Mesoproterozoic volcanic arc that was accreted onto the western margin of the Kaapvaal Craton during the ∼1.0–1.2 Ga Namaquan Orogeny. Sulfur isotope data (δ³⁴S) are presented for 57 sulfide separates and one barite sample from five massive sulfide occurrences in the Areachap Group. Although sulfides from each site have distinct sulfur isotope values, all δ³⁴S values fall within a very limited range (3.0‰ to 8.5‰). Barite has a δ³⁴S value of 18.5‰, very different from that of associated sulfides. At one of the studied sites (Kantienpan), a distinct increase in δ³⁴S of sulfides is observed from the massive sulfide lens into the disseminated sulfides associated with a distinct footwall alteration zone. Sulfide–sulfide and sulfide–barite mineral pairs which recrystallized together during amphibolite- and lower granulite facies metamorphism are not in isotopic equilibrium. Sulfur isotope characteristics of sulfides and sulfates of the Zn–Cu ores in the Areachap Group are, however, very similar to base metal sulfide accumulations associated with modern volcanic arcs and unsedimented mid-ocean ridges. It is thus concluded that profound recrystallization and textural reconstitution associated with high-grade regional metamorphism of the massive sulfide ores of the Areachap Group did not result in extensive sulfur isotopic homogenization. This is similar to observations in other metamorphosed VMS deposit districts and confirms that massive sulfide ores remain effectively a closed system for sulfur isotopes for both sulfides and sulfates during metamorphism.     

Petrology, isotope geochemistry and chemical budgets of oceanic gabbros-seawater interactions in the Equatorial Atlantic

 Petrological and chemical variations, as well as oxygen and strontium isotopic data are presented for metagabbros from the Romanche and Vema fracture zones. These rocks were affected by several types and degrees of alterations ranging from slight hydrothermal alteration to complete amphibolitization. Five major kinds of alteration processes ranging from late-magmatic deuteric alteration (stage I) to low temperature (<150 °C) alteration (stage V) were identified. Water-rock interactions between 300 and 650 °C are the most dominant interactions resulting in the most prevailing secondary mineralogical assemblages which characterize the amphibolite and/or greenschist facies (amphibole ± plagioclase ± epidote ± titanite ± chlorite ± prehnite). Hydrothermal alteration of these gabbroic rocks results in isotopic exchanges between rocks and seawater-derived fluids. These exchanges lead to decrease of gabbroic δ¹⁸O toward values as low as +3.9‰, and larger Sr isotopic variations than other oceanic gabbroic rocks (⁸⁷Sr/⁸⁶Sr ratios shift to 0.7029–0.7051). Calculation of a chemical budget indicates that metagabbros are hydrated and enriched in Fe and probably in Mg and Cl, while Si, Ca and Ti are released to the hydrothermal fluids. In addition to metamorphic recrystallization and geochemical transformation, hydrothermal alteration of oceanic gabbros contributes to the control of the global ocean geochemistry. Received: 8 March 1999 / Accepted: 12 July 1999     

Origin of the Maoduan Pb–Zn–Mo deposit, eastern Cathaysia Block, China: geological, geochronological, geochemical, and Sr–Nd–Pb–S isotopic constraints

The Maoduan Pb–Zn–Mo deposit is in hydrothermal veins with a pyrrhotite stage followed by a molybdenite and base metal stage. The Re–Os model ages of five molybdenite samples range from 138.6 ± 2.0 to 140.0 ± 1.9 Ma. Their isochron age is 137.7 ± 2.7 Ma. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) zircon U–Pb dating of the nearby exposed Linggen granite porphyry gave a ²⁰⁶Pb/²³⁸U age of 152.2 ± 2.2 Ma and the hidden Maoduan monzogranite yielded a mean of 140.0 ± 1.6 Ma. These results suggest that the intrusion of the Maoduan monzogranite and Pb–Zn–Mo mineralization are contemporaneous. δ ³⁴S values of sulfide minerals range from 3.4‰ to 4.8‰, similar to magmatic sulfur. Four sulfide samples have ²⁰⁶Pb/²⁰⁴Pb = 18.252–18.432, ²⁰⁷Pb/²⁰⁴Pb = 15.609–15.779, and ²⁰⁸Pb/²⁰⁴Pb = 38.640–39.431, similar to the age-corrected data of the Maoduan monzogranite. These isotope data support a genetic relationship between the Pb–Zn–Mo mineralization and the Maoduan monzogranite and probably indicate a common deep source. The Maoduan monzogranite has geochemical features similar to highly fractionated I-type granites, such as high SiO₂ (73.7–75.2 wt.%) and alkalis (K₂O + Na₂O = 7.8–8.9 wt.%) and low FeO_t (0.8–1.3 wt.%), MgO (~0.3 wt.%), P₂O₅ (~0.03 wt.%), and TiO₂ (~0.2 wt.%). The granitic rocks are enriched in Rb, Th, and U but depleted in Ba, Sr, Nb, Ta, P, and Ti. REE patterns are characterized by marked negative Eu anomalies (Eu/Eu^* = 0.2–0.4). The Maoduan monzogranite, having (⁸⁷Sr/⁸⁶Sr) _t  = 0.7169 to 0.7170 and ε_Nd(t) = −13.8 to −13.7, was probably derived from mixing of partial melts from enriched mantle and the Paleoproterozoic Badu group in an extensional tectonic setting.     

Origin of the Tongshankou porphyry–skarn Cu–Mo deposit,eastern Yangtze craton,Eastern China: geochronological,geochemical, and Sr–Nd–Hf isotopic constraints

The Tongshankou Cu–Mo deposit, located in the westernmost Daye district of the Late Mesozoic Metallogenic Belt along the Middle-Lower reaches of the Yangtze River, eastern China, consists mainly of porphyry and skarn ores hosted in the Tongshankou granodiorite and along the contact with the Lower Triassic marine carbonates, respectively. Sensitive high-resolution ion microprobe zircon U–Pb dating constrains the crystallization of the granodiorite at 140.6 ± 2.4 Ma (1σ). Six molybdenite samples from the porphyry ores yield Re–Os isochron age of 143.8 ± 2.6 Ma (2σ), while a phlogopite sample from the skarn ores yields an ⁴⁰Ar/³⁹Ar plateau age of 143.0 ± 0.3 Ma and an isochron age of 143.8 ± 0.8 Ma (2σ), indicating an earliest Cretaceous mineralization event. The Tongshankou granodiorite has geochemical features resembling slab-derived adakites, such as high Sr (740–1,300 ppm) and enrichment in light rare earth elements (REE), low Sc (<10 ppm), Y (<13.3 ppm), and depletion in heavy REE (<1.2 ppm Yb), and resultant high Sr/Y (60–92) and La/Yb (26–75) ratios. However, they differ from typical subduction-related adakites by high K, low MgO and Mg#, and radiogenic Sr–Nd–Hf isotopic compositions, with (⁸⁷Sr/⁸⁶Sr) _t  = 0.7062–0.7067, ɛ _Nd(t) = −4.37 to −4.63, (¹⁷⁶Hf/¹⁷⁷Hf) _t  = 0.282469–0.282590, and ɛ _Hf(t) = −3.3 to −7.6. The geochemical and isotopic data, coupled with geological analysis, indicate that the Tongshankou granodiorite was most likely generated by partial melting of enriched lithospheric mantle that was previously metasomitized by slab melts related to an ancient subduction system. Magmas derived from such a source could have acquired a high oxidation state, as indicated by the assemblage of quartz–magnetite–titanite–amphibole–Mg-rich biotite in the Tongshankou granodiorite and the compositions of magmatic biotite that fall in the field between the NiNiO and magnetite–hematite buffers in the Fe³⁺–Fe²⁺–Mg diagram. Sulfur would have been present as sulfates in such highly oxidized magmas, so that chalcophile elements Cu and Mo were retained as incompatible elements in the melt, contributing to subsequent mineralization. A compilation of existing data reveals that porphyry and porphyry-related Cu–Fe–Au–Mo mineralization from Daye and other districts of the Metallogenic Belt along the Middle-Lower reaches of the Yangtze River took place coevally in the Early Cretaceous and was related to an intracontinental extensional environment, distinctly different from the arc-compressive setting of the Cenozoic age that has been responsible for the emplacement of most porphyry Cu deposits of the Pacific Rim.     

Gold mineralization in the Mazowe area, Harare-Bindura-Shamva greenstone belt, Zimbabwe: II. Genetic relationships deduced from mineralogical, fluid inclusion and stable isotope studies, and the Sm-Nd isotopic composition of scheelites

In the Mazowe area some 40 km NW of Harare in Zimbabwe, gold mineralization is hosted in a variety of lithologies of the Archean Harare-Bindura-Shamva greenstone belt, in structures related to the late Archean regional D2/3 event. Conspicuous mineralzogical differences exist between the mines; the mainly granodiorite-hosted workings at Mazowe mine are on pyrite-rich reefs, mines of the Bernheim group have metabasalt host rocks and are characterized by arsenopyrite-rich ores, and Stori's Golden Shaft and Alice mine, both in metabasalts, work sulfide-poor quartz veins. In contrast to the mineralogical diversity, near-identical fluid inventories were found at the different mines. Both H₂O-CO₂-CH₄ fluids of low salinity, and highly saline fluids are present and are regarded to indicate fluid mixing during the formation of the deposits. Notably, these fluid compositions in the Mazowe gold field markedly contrast to ore fluids “typical” of Archean mesothermal gold deposits on other cratons. Stable isotope compositions of quartz from the various deposits (δ¹⁸O=10.8 to 13.2‰ SMOW), calcite (δ¹⁸O=9.5 to 11.9‰ SMOW and δ¹³C=−3.2 to −8.0‰ PDB), inclusion water (δD=−28 to −40‰ SMOW) and sulfides (δ³⁴S=1.3 to 3.2‰ CDT) are uniform within the range typical for Archean lode gold deposits worldwide. The fluid and stable isotope compositions support the statement that the mineralization in the Mazowe gold field formed from relatively reduced fluids with a “metamorphic” signature during a single event of gold mineralization. Microthermometric data further indicate that the deposits formed in the PT range of 1.65–2.3 kbar and 250–380 °C. Ages obtained by using the Sm/Nd and Rb/Sr isotope systems on scheelites are 2604 ± 84 Ma for the mineralization at Stori's Golden Shaft mine, and 2.40 ± 0.20 Ga for Mazowe mine. The Archean age at Stori's is regarded as close to the true age of gold mineralization in the area, whereas the Proterozoic age at Mazowe mine probably reflects later resetting. Received: 30 September 1998 / Accepted: 17 August 1999     

Re–Os dating and sulfur isotope composition of molybdenite from tungsten deposits in western Namaqualand, South Africa: implications for ore genesis and the timing of metamorphism

Both stratiform/stratabound and granite-related models have been used to explain the genesis of W(Mo) deposits in the Okiep copper district in western Namaqualand, South Africa. Apparently, stratabound mineralization (Fe-rich wolframite with accessory molybdenite) occurs in foliation-parallel quartz veins in high-grade (∼750 °C, 5–6 kbar) metapelites of the Wolfram Formation, and less commonly in small bodies of silicified leucogranites and pegmatites. Six Re–Os ages for molybdenites from four deposits (Nababeep Tungsten Far West, Kliphoog, Narrap, Tweedam) range between 1000 ± 4 and 1026 ± 5 Ma. These molybdenites define a well-constrained ¹⁸⁷Re–¹⁸⁷Os isochron with an age of 1019 ± 6 Ma, which is interpreted as the age of W(Mo) mineralization. This age is significantly younger than Proterozoic protolith ages for supracrustal rocks and the emplacement ages for the main intrusive suites, but geologic evidence requires overlap with a period of high-grade metamorphism. We suggest that W(Mo) mineralization is genetically linked to intra-crustal magmatic processes at ∼1020 Ma, thereby precluding the ∼1060 Ma Concordia granite as the source for mineralizing fluids. A narrow range of positive δ³⁴S compositions (+3.6 to +4.5‰) for eight molybdenites from five W(Mo) mines is consistent with a SO₂-rich fluid and a granite-related genetic model. Post-peak metamorphic deformation and metamorphism of W(Mo) ores is most likely related to the retrograde stage of the Namaquan orogeny, which overlaps emplacement of late-orogenic, evolved granites and pegmatites, and the formation of W(Mo) deposits in western Namaqualand. Therefore, the effects of retrograde Namaquan metamorphism extend at least to ∼1020 Ma or, alternatively, these W(Mo) veins were affected by a poorly constrained later event (e.g. early Pan-African). Received: 12 September 1999 / Accepted: 20 April 2000     

The influence of enclosing rock type on barite deposits, eastern Pyrenees, Spain: fluid inclusion and isotope (Sr, S, O, C) data

The Rocabruna and Coll de Pal barite deposits, located in the eastern Pyrenees of Spain, fill karstic cavities within carbonate rocks of Cambrian and Devonian age, respectively. The deposits contain barite, chalcopyrite, tetrahedrite, pyrite and minor sphalerite and galena with saddle dolomite and quartz as gangue. Fluid inclusion data from Coll de Pal quartz and dolomite indicate that the mineralizing fluid was a polysaline CaCl₂-rich brine, with temperatures between 125 and 150 °C. C and O isotopic compositions of carbonates in both deposits are consistent with a progressive increase in temperature during deposition. The ³⁴S values of barite, which range from 14.2 to 15.9‰ in Coll de Pal, and from 13.9 to 19.3‰ in Rocabruna, together with ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7118 to 0.7168 in Rocabruna, and from 0.7115 to 0.7136 in Coll de Pal, indicate two different fluid sources. We propose that these deposits formed as a result of mixing between a Ba-rich, sulfate-poor hot fluid, and sulfate-rich solutions of surficial origin. The different Sr isotope ratios in the deposits indicate that the hot Ba-rich fluids involved in each deposit were equilibrated with different rock types (carbonates and shales), in agreement with the geology of the two areas. Received: 22 October 1997 / Accepted: 24 March 1998     

Concordant ages for the giant Kipushi base metal deposit (DR Congo) from direct Rb–Sr and Re–Os dating of sulfides

We report concordant ages of 451.1 ± 6.0 and 450.5 ± 3.4 Ma from direct Rb–Sr and Re–Os isochron dating, respectively, of ore-stage Zn–Cu–Ge sulfides, including sphalerite for the giant carbonate-hosted Kipushi base metal (+Ge) deposit in the Neoproterozoic Lufilian Arc, DR Congo. This is the first example of a world-class sulfide deposit being directly dated by two independent isotopic methods. The 451 Ma age for Kipushi suggests that the ore-forming solutions did not evolve from metamorphogenic fluids mobilized syntectonically during the Pan-African-Lufilian orogeny but rather were generated in a Late Ordovician postorogenic, extensional setting. The homogeneous Pb isotopic composition of the sulfides indicates that both Cu–Ge- and Zn-rich orebodies of the Kipushi deposit formed contemporaneously from the same fluid system. The sulfide Pb isotope signatures in combination with initial ⁸⁷Sr/⁸⁶Sr and ¹⁸⁷Os/¹⁸⁸Os ratios defined by the isochrons point to metal sources located in the (upper) crust. The concordant Re–Os and Rb–Sr ages obtained in this study provide independent proof of the geological significance of direct Rb–Sr dating of sphalerite.     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.     

Late Cretaceous porphyry Cu and epithermal Cu–Au association in the Southern Panagyurishte District,Bulgaria: the paired Vlaykov Vruh and Elshitsa deposits

Vlaykov Vruh–Elshitsa represents the best example of paired porphyry Cu and epithermal Cu–Au deposits within the Late Cretaceous Apuseni–Banat–Timok–Srednogorie magmatic and metallogenic belt of Eastern Europe. The two deposits are part of the NW trending Panagyurishte magmato-tectonic corridor of central Bulgaria. The deposits were formed along the SW flank of the Elshitsa volcano-intrusive complex and are spatially associated with N110-120-trending hypabyssal and subvolcanic bodies of granodioritic composition. At Elshitsa, more than ten lenticular to columnar massive ore bodies are discordant with respect to the host rock and are structurally controlled. A particular feature of the mineralization is the overprinting of an early stage high-sulfidation mineral assemblage (pyrite ± enargite ± covellite ± goldfieldite) by an intermediate-sulfidation paragenesis with a characteristic Cu–Bi–Te–Pb–Zn signature forming the main economic parts of the ore bodies. The two stages of mineralization produced two compositionally different types of ores—massive pyrite and copper–pyrite bodies. Vlaykov Vruh shares features with typical porphyry Cu systems. Their common geological and structural setting, ore-forming processes, and paragenesis, as well as the observed alteration and geochemical lateral and vertical zonation, allow us to interpret the Elshitsa and Vlaykov Vruh deposits as the deep part of a high-sulfidation epithermal system and its spatially and genetically related porphyry Cu counterpart, respectively. The magmatic–hydrothermal system at Vlaykov Vruh–Elshitsa produced much smaller deposits than similar complexes in the northern part of the Panagyurishte district (Chelopech, Elatsite, Assarel). Magma chemistry and isotopic signature are some of the main differences between the northern and southern parts of the district. Major and trace element geochemistry of the Elshitsa magmatic complex are indicative for the medium- to high-K calc-alkaline character of the magmas. ⁸⁷Sr/⁸⁶Sr_(i) ratios of igneous rocks in the range of 0.70464 to 0.70612 and ¹⁴³Nd/¹⁴⁴Nd_(i) ratios in the range of 0.51241 to 0.51255 indicate mixed crustal–mantle components of the magmas dominated by mantellic signatures. The epsilon Hf composition of magmatic zircons (+6.2 to +9.6) also suggests mixed mantellic–crustal sources of the magmas. However, Pb isotopic signatures of whole rocks (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.64, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.64, and ²⁰⁸Pb/²⁰⁴Pb = 37.69–38.56) along with common inheritance component detected in magmatic zircons also imply assimilation processes of pre-Variscan and Variscan basement at various scales. U–Pb zircon and rutile dating allowed determination of the timing of porphyry ore formation at Vlaykov Vruh (85.6 ± 0.9 Ma), which immediately followed the crystallization of the subvolcanic dacitic bodies at Elshitsa (86.11 ± 0.23 Ma) and the Elshitsa granite (86.62 ± 0.02 Ma). Strontium isotope analyses of hydrothermal sulfates and carbonates (⁸⁷Sr/⁸⁶Sr = 0.70581–0.70729) suggest large-scale interaction between mineralizing fluids and basement lithologies at Elshitsa–Vlaykov Vruh. Lead isotope compositions of hydrothermal sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.432–18.534, ²⁰⁷Pb/²⁰⁴Pb = 15.608–15.647, and ²⁰⁸Pb/²⁰⁴Pb = 37.497–38.630) allow attribution of ore-formation in the porphyry and epithermal deposits in the Southern Panagyurishte district to a single metallogenic event with a common source of metals.     

Sulfur isotope variations from orebody to hand-specimen scale at the Mežica lead–zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb–Zn ore district at Mežica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mežica covers an area of 64 km² with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have δ ³⁴ S values in the range of –24.7 to –1.5‰ VCDT (–13.5 ± 5.0‰) and –24.7 to –1.4‰ (–10.7 ± 5.9‰), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide δ ³⁴ S values are negative within a broad range, with δ ³⁴ S _pyrite <δ ³⁴ S _sphalerite <δ ³⁴ S _galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H₂S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of ³⁴S-enriched H₂S to the ore fluid. The variations of δ ³⁴ S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative δ ³⁴ S values with time along the different sphalerite generations are consistent with mixing of different H₂S sources, with a decreasing contribution of H₂S from regional TSR, and an increase from a local H₂S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (–11.9 to –1.7‰; –7.0 ± 2.7‰, n = 12) tends to be depleted in ³⁴ S compared with conformable ore (–24.7 to –2.8‰, –11.7 ± 6.2‰, n = 39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide δ ³⁴ S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H₂S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H₂S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.     

Metamorphism, isotopic ages and composition of lower crustal granulite xenoliths from the Cretaceous Salta Rift, Argentina

Crustal xenoliths from basanitic dikes and necks that intruded into continental sediments of the Cretaceous Salta Rift at Quebrada de Las Conchas, Provincia Salta, Argentina were investigated to get information about the age and the chemical composition of the lower crust. Most of the xenoliths have a granitoid composition with quartz-plagioclase-garnet-rutile ± K-feldspar as major minerals. The exceedingly rare mafic xenoliths consist of plagioclase-clinopyroxene-garnet ± hornblende. All xenoliths show a well equilibrated granoblastic fabric and the minerals are compositionally unzoned. Thermobarometric calculations indicate equilibration of the mafic xenoliths in the granulite facies at temperatures of ca. 900 °C and pressures of ca. 10 kbar. The Sm-Nd mineral isochron ages are 95.1 ± 10.4 Ma, 91.5 ± 13.0 Ma, 89.0 ± 4.2 Ma (granitoid xenoliths), and 110.7 ± 23.6 Ma (mafic xenolith). These ages are in agreement with the age of basanitic volcanism (ca. 130–100 and 80–75 Ma) and are interpreted as minimum ages of metamorphism. Lower crustal temperature at the time given by the isochrons was above the closure temperature of the Sm-Nd system (>600–700 °C). The Sm-Nd and Rb-Sr isotopic signatures (¹⁴⁷Sm/¹⁴⁴Nd = 0.1225–0.1608; ¹⁴³Nd/¹⁴⁴Nd_{t 0} = 0.512000–0.512324; ⁸⁷Rb/⁸⁶Sr = 0.099–0.172; ⁸⁷Sr/⁸⁶Sr_{t 0} = 0.708188–0.7143161) and common lead isotopic signatures (²⁰⁶Pb/²⁰⁴Pb = 18.43–18.48; ²⁰⁷Pb/²⁰⁴Pb = 15.62–15.70; ²⁰⁸Pb/²⁰⁴Pb = 38.22 –38.97) of the granitoid xenoliths are indistinguishable from the isotopic composition of the Early Paleozoic metamorphic basement from NW Argentina, apart from the lower ²⁰⁸Pb/²⁰⁴Pb ratio of the basement. The Sm-Nd depleted mantle model ages of ca. 1.8 Ga from granitoid xenoliths and Early Paleozoic basement point to a similar Proterozoic protolith. Time constraints, the well equilibrated granulite fabric, P-T conditions and lack of chemical zoning of minerals point to a high temperature in a crust of nearly normal thickness at ca. 90 Ma and to a prominent thermal anomaly in the lithosphere. The composition of the xenoliths is similar to the composition of the Early Paleozoic basement in the Andes of NW Argentina and northern Chile. A thick mafic lower crust seems unlikely considering low abundance of mafic xenoliths and the predominance of granitoid xenoliths. Received: 21 July 1998 / Accepted: 27 October 1998     

From basalt to dacite: origin and evolution of the calc-alkaline series of Salina, Aeolian Arc, Italy

The island of Salina comprises one of the most distinct calc-alkaline series of the Aeolian arc (Italy), in which calc-alkaline, high-K calc-alkaline, shoshonitic and leucite-shoshonitic magma series are developed. Detailed petrological, geochemical and isotopic (Sr, Nd, Pb, O) data are reported for a stratigraphically well-established sequence of lavas and pyroclastic rocks from the Middle Pleistocene volcanic cycle (430–127 ka) of Salina, which is characterized by an early period of basaltic volcanism (Corvo; Capo; Rivi; Fossa delle Felci, group 1) and a sequence of basaltic andesites, and andesites and dacites in the final stages of activity (Fossa delle Felci, groups 2–8). Major and trace element compositional trends, rare earth element (REE) abundances and mineralogy reveal the importance of crystal fractionation of plagioclase + clinopyroxene + olivine/ orthopyroxene ± titanomagnetite ± amphibole ± apatite in generating the more evolved magma types from parental basaltic magmas, and plagioclase accumulation in producing the high Al₂O₃ contents of some of the more evolved basalts. Sr isotope ratios range from 0.70410 to 0.70463 throughout the suite and show a well-defined negative correlation with ¹⁴³Nd/¹⁴⁴Nd (0.51275–0.51279). Pb isotope compositions are distinctly radiogenic with relatively large variations in ²⁰⁶Pb/²⁰⁴Pb (19.30–19.66), fairly constant ²⁰⁷Pb/²⁰⁴Pb (15.68–15.76) and minor variations in ²⁰⁸Pb/²⁰⁴Pb ratios (39.15–39.51). Whole-rock δ¹⁸O values range from +6.4 to +8.5‰ and correlate positively with Sr isotope ratios. Overall, the isotopic variations are correlated with the degree of differentiation of the rocks, indicating that only small degrees of crustal assimilation are overprinting the dominant evolution by crystal–liquid fractionation (AFC-type processes). The radiogenic and oxygen isotope composition of the Salina basalts suggests derivation from primary magmas from a depleted mantle source contaminated by slab-derived fluids and subducted sediments with an isotopic signature of typical upper continental crust. These magmas then evolved further to andesitic and dacitic compositions through the prevailing process of low-pressure fractional crystallization in a shallow magma reservoir, accompanied by minor assimilation of crustal lithologies similar to those of the Calabrian lower crust. Received: 29 November 1999 / Accepted: 16 April 2000     

Dating multiply overprinted Sn-mineralized granites—examples from the Erzgebirge,Germany

Granites and primary tin mineralization in the Erzgebirge were dated using (1) conventional U–Pb dating of uraninite inclusions in mica, (2) Rb–Sr dating of inclusions in quartz that represent highly evolved melts, (3) Re–Os dating of magmatic–hydrothermal molybdenite, and (4) chemical Th–U–Pb dating of uraninite. Conventional isotope dilution and thermal ion mass spectrometry and chemical Th–U–Pb dating of uraninite in granites from the Ehrenfriedersdorf mining district provide ages of 323.9 ± 3.5 Ma (2σ; Greifenstein granite) and 320.6 ± 1.9 and 319.7 ± 3.4 Ma (2σ, both Sauberg mine), in agreement with U–Pb apatite ages of 323.9 ± 2.9 and 317.3 ± 1.6 Ms (2σ, both Sauberg mine). Rb–Sr analysis of melt inclusions from Zinnwald gives highly radiogenic Sr isotopic compositions that, with an assumed initial Sr isotopic composition, permit calculation of precise ages from single inclusions. The scatter of the data indicates that some quartz-hosted melt inclusions have been affected by partial loss of fluid exsolved from the melt inclusion. Re–Os dating of two molybdenite samples from Altenberg provides ages of 323.9 ± 2.5 and 317.9 ± 2.4 Ma (2σ). Together with age data from the literature, our new ages demonstrate that primary tin mineralization and the emplacement of the large Sn-specialized granites in the Erzgebirge fall in a narrow range between 318 and 323 Ma. Primary Sn mineralization occurred within a short interval during post-collisional collapse of the Variscan orogen and was essentially synchronous over the entire Erzgebirge. In contrast to earlier claims, no systematic age difference between granites of the eastern and western Erzgebirge was established. Furthermore, our data do not support a large age range for Late-Variscan granites of the Erzgebirge (330–290 Ma), as has been previously suggested.