Hydrothermal gold mineralization at the Hira Buddini gold mine,India: constraints on fluid evolution and fluid sources from boron isotopic compositions of tourmaline

We determined the boron isotope and chemical compositions of tourmaline from the Hira Buddini gold deposit within the Archean Hutti-Maski greenstone belt in southern India to investigate the evolution of the hydrothermal system and to constrain its fluid sources. Tourmaline is a minor but widespread constituent in the inner and distal alteration zones of metabasaltic and metadacite host rocks associated with the hydrothermal gold mineralization. The Hira Buddini tourmaline belongs to the dravite–schorl series with variations in Al, Fe/(Fe+Mg), Ca, Ti, and Cr contents that can be related to their host lithology. The total range of δ¹¹B values determined is extreme, from −13.3‰ to +9.0‰, but 95% of the values are between −4 and +9‰. The boron isotope compositions of metabasalt-hosted tourmaline show a bimodal distribution with peak δ¹¹B values at about −2‰ and +6‰. The wide range and bimodal distribution of boron isotope ratios in tourmaline require an origin from at least two isotopically distinct fluid sources, which entered the hydrothermal system separately and were subsequently mixed. The estimated δ¹¹B values of the hydrothermal fluids, based on the peak tourmaline compositions and a mineralization temperature of 550°C, are around +1 and +10‰. The isotopically lighter of the two fluids is consistent with boron released by metamorphic devolatilization reactions from the greenstone lithologies, whereas the ¹¹B-rich fluid is attributed to degassing of I-type granitic magmas that intruded the greenstone sequence, providing heat and fluids to the hydrothermal system. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Detrital,metamorphic and metasomatic tourmaline in high-pressure metasediments from Syros (Greece): intra-grain boron isotope patterns determined by secondary-ion mass spectrometry

The boron isotopic composition of zoned tourmaline in two metasediments from the island of Syros, determined by secondary-ion mass spectrometry (SIMS), reflects the sedimentary and metamorphic record of the rocks. Tourmaline from a silicate-bearing marble contains small (≤20 μm) detrital cores with highly variable δ ¹¹B values (−10.7 to +3.6‰), pointing to a heterogeneous protolith derived from multiple sources. The sedimentary B isotopic record survived the entire metamorphic cycle with peak temperatures of ∼500°C. Prograde to peak metamorphic rims are homogeneous and similar among all analysed grains (δ ¹¹B ≈ +0.9‰). The varying δ ¹¹B values of detrital cores in the siliceous marble demonstrate that in situ B isotope analysis of tourmaline by SIMS is a potentially powerful tool for provenance studies not only in sediments but also in metasediments. A meta-tuffitic blueschist bears abundant tourmaline with dravitic cores of detrital or authigenic origin (δ ¹¹B ≈ −3.3‰), and prograde to peak metamorphic overgrowth zones (−1.6‰). Fe-rich rims, formed during influx of B-bearing fluids under retrograde conditions, show strongly increasing δ ¹¹B values (up to +7.7‰) towards the margins of the grains. The δ ¹¹B values of metamorphic tourmaline from Syros, formed in mixed terrigenous–marine sediments, reflect the B signal blended from these two different sources, and was probably not altered by dehydration during subduction.     

Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rocks: the Erongo granite and tourmalinites in the Damara Belt,Namibia

Tourmaline is widespread in metapelites and pegmatites from the Neoproterozoic Damara Belt, which form the basement and potential source rocks of the Cretaceous Erongo granite. This study traces the B-isotope variations in tourmalines from the basement, from the Erongo granite and from its hydrothermal stage. Tourmalines from the basement are alkali-deficient schorl-dravites, with B-isotope ratios typical for continental crust (δ¹¹B average −8.4‰ ± 1.4, n = 11; one sample at −13‰, n = 2). Virtually all tourmaline in the Erongo granite occurs in distinctive tourmaline-quartz orbicules. This “main-stage” tourmaline is alkali-deficient schorl (20–30% X-site vacancy, Fe/(Fe + Mg) 0.8–1), with uniform B-isotope compositions (δ¹¹B −8.7‰ ± 1.5, n = 49) that are indistinguishable from the basement average, suggesting that boron was derived from anatexis of the local basement rocks with no significant shift in isotopic composition. Secondary, hydrothermal tourmaline in the granite has a bimodal B-isotope distribution with one peak at about −9‰, like the main-stage tourmaline, and a second at −2‰. We propose that the tourmaline-rich orbicules formed late in the crystallization history from an immiscible Na–B–Fe-rich hydrous melt. The massive precipitation of orbicular tourmaline nearly exhausted the melt in boron and the shift of δ¹¹B to −2‰ in secondary tourmaline can be explained by Rayleigh fractionation after about 90% B-depletion in the residual fluid. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Tourmaline geochemistry and δ<Superscript>11</Superscript>B variations as a guide to fluid–rock interaction in the Habachtal emerald deposit,Tauern Window,Austria

Tourmalines from the Habachtal emerald deposit in the Eastern Alps formed together with emerald in a ductile shear zone during blackwall metasomatism between pelitic country rocks and a serpentinite body. Electron microprobe and secondary ion mass spectrometric (SIMS) analyses provide a record of chemical and B-isotope variations in tourmalines which represent an idealized profile from metapelites into the blackwall sequence of biotite and chlorite schists. Tourmaline is intermediate schorl-dravite in the country rock and become increasingly dravitic in the blackwall zones, while F and Cr contents increase and Al drops. Metasomatic tourmaline from blackwall zones is typically zoned optically and chemically, with rim compositions rich in Mg, Ti, Ca and F compared with the cores. The total range in δ¹¹B values is −13.8 to −5.1‰ and the within-sample variations are typically 3–5‰. Both of these ranges are beyond the reach of closed-system fractionation at the estimated 500–550°C conditions of formation, and at least two boron components with contrasting isotopic composition are indicated. A key observation from tourmaline core analyses is a systematic shift in δ¹¹B from the country rock (−14 to −10‰) to the inner blackwall zones (−9 to −5‰). We suggest that two separate fluids were channeled and partially mixed in the Habachtal shear zone during blackwall alteration and tourmaline-emerald mineralization. A regional metamorphic fluid carried isotopically light boron as observed in the metapelite country rocks. The other fluid is derived from the serpentinite association and has isotopically heavier boron typical for MORB or altered oceanic crust. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mineral Chemistry and Boron Isotopic Composition of Tourmaline from the Devonian Metallogenic District of Shanyang-Zhashui,Eastern Qinling

Toumaline is widespread in the host strata of strata-bound base metal sulphide deposits in the Devonian metallogenic district around Shanyang-Zhashui in eastern Qinling. As a member of the schorl-dravite series, the tourmaline is characterized by Mg > Fe and Na > Ca, showing apparent chemical zonation which records the geochemistry during its formation and subsequent regional metamorphism and hydrothermal overprint. The close similarity in chemical and isotopic constitutions between the tourmaline of the main metallogenic epoch in this district [FeO/(FeO + MgO)=0.34 − 0.39 and δ¹¹B=−7.6‰ − − 8.8‰] and those related to massive sulphide deposits typical of submarine (exhalative) hydrothermal sedimentation may add further support to a similar mechanism of mineralization for the strata-bound deposits in the district. Supported by the Foundation for Young Scientists under the National Natural Science Foundation of China.     

Tourmaline in Proterozoic Massive Sulfide Deposits from Rajasthan, India

We have analyzed the chemical composition and boron isotope composition of tourmaline from tourmalinites, granite and a quartz-tourmaline vein from the Deri ore zone and from a pegmatitic band in the Rampura-Agucha ore body. These two Proterozoic massive sulfide deposits occur in the Aravalli-Delhi orogenic belt, Rajasthan, northwest India. Tourmaline from stratiform tourmalinites closely associated with the massive sulfides in the Deri deposit have preserved their original chemical compositions despite regional and thermal metamorphism in the area. These tourmalines have low Fe/(Fe + Mg) ratios (0.19–0.30; mean 0.26) that suggest formation close to the sediment-sea water interface. The δ¹¹B values (−15.5 and −16.4‰) are compatible with boron derived from leaching of argillaceous sediments and/or felsic volcanics underlying the original massive sulfide deposit during its formation. Boron isotope compositions measured in tourmaline from a post-ore granite and quartz-tourmaline vein in the Deri deposit indicate that boron in these tourmalines was derived from the tourmalinites produced during ore formation. The boron isotope systematics of a coarse brown tourmaline crystal from a pegmatitic band on the hanging wall contact of the Rampura-Agucha deposit indicate that 45 ± 25% of the boron within the original tourmaline was lost during upper amphibolite facies regional metamorphism. Received: 3 April 1996 / Accepted: 11 April 1996     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Stable isotope characteristics and origin of ore-forming fluids in copper-gold-polymetallic deposits within strike-slip pull-apart basin of Weishan-Yongping continental collision orogenic belt, Yunnan Province, China

More than 140 middle-small sized deposits or minerals are present in the Weishan-Yongping ore concentration area which is located in the southern part of a typical Lanping strike-slip and pull-apart basin. It has plenty of mineral resources derived from the collision between the Indian and Asian plates. The ore-forming fluid system in the Weishan-Yongping ore concentration area can be divided into two subsystems, namely, the Zijinshan subsystem and Gonglang arc subsystem. The ore-forming fluids of Cu, Co deposits in the Gonglang arc fluid subsystem have δD values between −83.8‰ and −69‰, δ¹⁸O values between 4.17‰ and 10.45‰, and δ¹³C values between −13.6‰ and 3.7‰, suggesting that the ore-forming fluids of Cu, Co deposits were derived mainly from magmatic water and partly from formation water. The ore-forming fluids of Au, Pb, Zn, Fe deposits in the Zijinshan subsystem have δD values between −117.4‰ and −76‰, δ¹⁸O values between 5.32‰ and 9.56‰, and Δ¹³C values between −10.07‰ and −1.5‰. The ore-forming fluids of Sb deposits have δD values between −95‰ and −78‰, δ¹⁸O values between 4.5‰ and 32.3‰, and Δ¹³C values between −26.4‰ and −1.9‰. Hence, the ore-forming fluids of the Zijinshan subsystem must have been derived mainly from formation water and partly from magmatic water. Affected by the collision between the Indian and Asian plates, ore-forming fluids in Weishan-Yongping basin migrated considerably from southwest to northeast. At first, the Gonglang arc subsystem with high temperature and high salinity was formed. With the development of the ore-forming fluids, the Zijinshan subsystem with lower temperature and lower salinity was subsequently formed. Translated from Mineral Deposits, 2006, 25(1): 60–70 [译自: 矿床地质]     

An intrusion-related origin for Cu–Au mineralization in iron oxide–copper–gold (IOCG) provinces

Major Cu–Au deposits of iron oxide–copper–gold (IOCG) style are temporally associated with oxidized, potassic granitoids similar to those linked to major porphyry Cu–Au deposits. Stable and radiogenic isotope evidence indicates fluids and ore components were likely sourced from the intrusions. IOCG deposits form over a range of crustal levels because CO₂-rich fluids separate from the magmas at higher pressures than in CO₂-poor systems, thereby, promoting partitioning of H₂O, Cl and metals to the fluid phase. At deep levels, the magma–fluid system cannot generate sufficient mechanical energy to fracture the host rocks as in porphyry systems and the IOCG deposits therefore form in a variety of fault-related structural traps where the magmatic fluids may mix with other fluids to promote ore formation. At shallow levels, the IOCG deposits form breccia and fracture-hosted mineralization styles similar to the hydrothermal intrusive breccias and sulphide vein systems that characterize many porphyry Cu–Au deposits. The fluids associated with IOCG deposits are typically H₂O–CO₂–salt fluids that evolve by unmixing of the carbonic phase and by mixing with fluids from other sources. In contrast, fluids in porphyry systems typically evolve by boiling of moderate salinity fluid to produce high salinity brine and a vapor phase commonly with input of externally derived fluids. These different fluid compositions and mechanisms of evolution lead to different alteration types and parageneses in porphyry and IOCG deposits. Porphyry Cu–Au deposits typically evolve through potassic, sericitic and (intermediate and/or advanced) argillic stages, while IOCG deposits typically evolve through sodic(–calcic), potassic and carbonate-rich stages, and at deeper levels, generally lack sericitic and argillic alteration. The common association of porphyry and IOCG Cu–Au deposits with potassic, oxidized intermediate to felsic granitoids, together with their contrasting fluid compositions, alteration styles and parageneses suggest that they should be considered as part of the broad family of intrusion-related systems but that they are typically not directly related to each other.     

Origin of fluids in iron oxide–copper–gold deposits: constraints from δ 37Cl, 87Sr/86Sri and Cl/Br

The origin of the hypersaline fluids (magmatic or basinal brine?), associated with iron oxide (Cu–U–Au–REE) deposits, is controversial. We report the first chlorine and strontium isotope data combined with Cl/Br ratios of fluid inclusions from selected iron oxide–copper–gold (IOCG) deposits (Candelaria, Raúl–Condestable, Sossego), a deposit considered to represent a magmatic end member of the IOCG class of deposit (Gameleira), and a magnetite–apatite deposit (El Romeral) from South America. Our data indicate mixing of a high δ ³⁷Cl magmatic fluid with near 0‰ δ ³⁷Cl basinal brines in the Candelaria, Raúl–Condestable, and Sossego IOCG deposits and leaching of a few weight percent of evaporites by magmatic-hydrothermal (?) fluids at Gameleira and El Romeral. The Sr isotopic composition of the inclusion fluids of Candelaria, Raúl–Condestable, and El Romeral confirms the presence of a non-magmatic fluid component in these deposits. The heavy chlorine isotope signatures of fluids from the IOCG deposits (Candelaria, Raúl–Condestable, Sossego), reflecting the magmatic-hydrothermal component of these fluids, contrast with the near 0‰ δ ³⁷Cl values of porphyry copper fluids known from the literature. The heavy chlorine isotope compositions of fluids of the investigated IOCG deposits may indicate a prevailing mantle Cl component in contrast to porphyry copper fluids, an argument also supported by Os isotopes, or could result from differential Cl isotope fractionation processes (e.g. phase separation) in fluids of IOCG and porphyry Cu deposits.     

Isotopic composition of dissolved boron and its geochemical behavior in a freshwater-seawater mixture at the estuary of the Changjiang （Yangtze） River

The isotopic composition of dissolved boron, in combination with the elemental concentrations of B, Cl and salinities in freshwater-seawater mixed samples taken from the estuary of the Changjiang River, the largest one in China, was investigated in detail in this study. Brackish water and seawater samples from the estuary of the Changjiang River were collected during low water season in November, 1998. Boron isotopic compositions were determined by the Cs2BO^＋2-graphite technique with a analytical uncertainty of 0.2‰ for NIST SRM 951 and an average analytical uncertainty of 0.8‰ for the samples. The isotopic compositions of boron, expressed in δ^11B, and boron concentrations in the Changjiang River at Nanjing and seawater from the open marine East Sea, China, are characterized by δ^11B values of -5.4‰ and 40.0‰, as well as 0.0272 and 4.43 mg B/L, respectively. Well-defined correlations between δ^11B values, B concentrations and Cl concentrations are interpreted in terms of binary mixing between fiver input water and East Sea seawater by a process of straightforward dilution. The offsets of δ^11B values are not related to the contents of clastic sediment and to the addition of boron. These relationships favor a conservative behavior of boron at the estuarine of the Changjiang River.     

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     

The La Unión Au ± Cu prospect,Camagüey District,Cuba: fluid inclusion and stable isotope evidence for ore-forming processes

The Camagüey district, Cuba, is known for its epithermal precious metal deposits in a Cretaceous volcanic arc setting. Recently, the La Unión prospect was discovered in the southern part of the district, containing gold and minor copper mineralization interpreted as porphyry type. Mineralization is hosted in a 73.0 ± 1.5 Ma calc–alkaline I-type oxidized porphyry quartz diorite intrusive within volcanic and volcaniclastic rocks of the early Cretaceous Guáimaro Formation. The porphyry is affected by propylitic alteration and crosscut by a network of quartz and carbonate veinlets and veins. Chlorite, epidote, sericite, quartz, and pyrite are the main minerals in the early veins which are cut by late carbonate and zeolite veins. Late barite pseudomorphously replaces pyrite. Gold is associated with pyrite as disseminations in the altered quartz diorite and in the veins, occurring as inclusions or filling fractures in pyrite with 4 g/t Au in bulk samples, and up to 900 ppm Au in in pyrite. Fluid inclusion and oxygen isotope data are consistent with a H₂O–NaCl–(KCl) mineralizing fluid, derived from the quartz diorite magma, and trapped at least at 425°C and 1.2 kbar. This primary fluid unmixed into two fluid phases, a hypersaline aqueous fluid and a low-salinity vapor-rich fluid. Boiling during cooling may have played an important role in metal precipitation. Pyrite δ³⁴S values for the La Unión prospect range between 0.71‰ and 1.31‰, consistent with a homogeneous magmatic sulfur source. The fluids in equilibrium with the mineralized rocks have estimated δ¹⁸O values from 8‰ to 11.8‰, calculated for a temperature range of 480–505°C. The tectonic environment of the La Unión prospect, its high gold and low copper contents, the physical–chemical characteristics of the mineralizing fluids and the isotopic signature of the alteration minerals and fluids indicate that the La Unión gold mineralization is similar to the porphyry gold type, even though the ore-related epidote–chlorite alteration can be classified as propylitic and not the classic potassic and/or phyllic alteration. The low copper contents in the prospect could be due to a mineralizing fluid previously saturated in copper, which is indicated by trapped chalcopyrite crystals in high-temperature fluid inclusions. The low-temperature paragenesis, represented by carbonate, zeolite and barite, indicates epithermal overprint. The study shows the potential for other gold porphyry-type deposits in the Cretaceous volcanoplutonic arc of Cuba.     

Boron isotopic composition of tourmaline from massive sulfide deposits and tourmalinites

Boron isotope ratios (¹¹B/¹⁰B) have been measured on 60 tourmaline separates from over 40 massive sulfide deposits and tourmalinites from a variety of geologic and tectonic settings. The coverage of these localities is global (5 continents) and includes the giant ore bodies at Kidd Creek and Sullivan (Canada), Broken Hill (Australia), and Ducktown (USA). Overall, the tourmalines display a wide range in ¹¹B values from –22.8 to +18.3 Possible controls over the boron isotopic composition of the tourmalines include: 1) composition of the boron source, 2) regional metamorphism, 3) water/rock ratios, 4) seawater entrainment, 5) temperature of formation, and 6) secular variations in seawater ¹¹B. The most significant control appears to be the composition of the boron source, particularly the nature of footwall lithologies; variations in water/ rock ratios and seawater entrainment are of secondary importance. The boron isotope values seem especially sensitive to the presence of evaporites (marine and non-marine) and carbonates in source rocks to the massive sulfide deposits and tourmalinites.     

Boron-isotope fractionation between tourmaline and fluid: an experimental re-investigation

The fractionation of boron isotopes between synthetic dravitic tourmaline and fluid was determined by hydrothermal experiments between 400 and 700°C at 200 MPa and at 500°C, 500 MPa. Tourmaline was crystallized from an oxide mix in presence of water that contained boron in excess. In one series of experiments, [B]_fluid/[B]_tour was 9 after the run; in another series it was 0.1. All experiments produced tourmaline as the sole boron-bearing solid, along with traces of quartz and talc. Powder XRD and Rietveld refinements revealed no significant amounts of tetrahedrally coordinated boron in tourmaline. ¹¹B always preferentially fractionated into the fluid. For experiments where [B]_fluid/[B]_tour was 9, a consistent temperature-dependent boron isotope fractionation curve resulted, approximated by Δ¹¹B_{(tour–fluid)} = −4.20 · [1,000/T (K)] + 3.52; R ² = 0.77, and valid from 400 to 700°C. No pressure dependence was observed. The fractionation (−2.7 ± 0.5‰ at 400°C; and −0.8 ± 0.5‰ at 700°C) is much lower than that previously presented by Palmer et al. (1992). Experiments where [B]_fluid/[B]_tour was 0.1 showed a significant larger apparent fractionation of up to −4.7‰. In one of these runs, the isotopic composition of handpicked tourmaline crystals of different size varied by 1.3‰. This is interpreted as resulting from fractional crystallization of boron isotopes during tourmaline growth due to the small boron reservoir of the fluid relative to tourmaline, thus indicating larger fractionation than observed at equilibrium. The effect is eliminated or minimized in experiments with very high boron excess in the fluid. We therefore suggest that values given by the above relation represent the true equilibrium fractionations.     

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.     

Pleistocene recycling of copper at a porphyry system,Atacama Desert,Chile: Cu isotope evidence

We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ⁶⁵Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ⁶⁵Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.     

Sulfur isotopic zonation in the Cadia district,southeastern Australia: exploration significance and implications for the genesis of alkalic porphyry gold–copper deposits

The alkalic porphyry gold–copper deposits of the Cadia district occur in the eastern Lachlan Fold Belt of New South Wales, Australia. The district comprises four porphyry deposits (Ridgeway, Cadia Quarry, Cadia Hill, and Cadia East) and two iron–copper–gold skarn deposits (Big Cadia and Little Cadia). Almost 1,000 tonnes of contained gold and more than four million tonnes of copper have been discovered in these systems, making Cadia the world’s largest known alkalic porphyry district, in terms of contained gold. Porphyry gold–copper ore at Cadia is associated with quartz monzonite intrusive complexes, and is hosted by central stockwork and sheeted quartz–sulfide–(carbonate) vein systems. The Cadia porphyry deposits are characterized by cores of potassic and/or calc–potassic alteration assemblages, and peripheral halos of propylitic alteration, with late-stage phyllic alteration mostly restricted to fault zones. Hematite dusting is an important component of the propylitic alteration assemblage, and has produced a distinctive reddening of feldspar minerals in the volcanic wall rocks around the mineralized centers. Sulfide mineralization is strongly zoned at Ridgeway and Cadia East, with bornite-rich cores surrounded by chalcopyrite-rich halos and peripheral zones of pyrite mineralization. The Cadia Hill and Cadia Quarry deposits have chalcopyrite-rich cores and pyrite-rich halos, and Cadia Hill contains a high-level bornite-rich zone. Distinctive sulfur isotopic zonation patterns have been identified at Ridgeway, Cadia Hill, and Cadia East. The deposit cores are characterized by low δ³⁴S_sulfide values (−10 to −4‰), consistent with sulfide precipitation from an oxidized (sulfate-predominant) magmatic fluid at 450 to 400°C. Pyrite grains that occur in the propylitic alteration halos typically have δ³⁴S_sulfide values near 0‰. There is a gradual increase in δ³⁴S_sulfide values outwards from the deposit cores through the propylitic halos. Water–rock interaction during propylitic alteration caused magmatic sulfate reduction and concomitant oxidation of ferrous iron-bearing minerals, resulting in enrichment of ³⁴S in pyrite and also producing the distinctive reddened, hematite-rich alteration halos to the Cadia deposits. These results show that sulfur isotope analyses have potential applications in the exploration of alkalic porphyry-style deposits, with zones of depleted δ³⁴S_sulfide values most prospective for high-grade mineralization.     

Tourmaline in the Vetka porphyry copper-molybdenum deposit of the Chukchi Peninsula of Russia

Three generations of tourmaline have been identified in propylite in the Vetka porphyry copper-molybdenum deposit of the Chukchi Peninsula of Russia. Tourmaline-I is characterized by its Fe_tot/(Fe_tot + Mg) value, which ranges from 0.33 to 0.49. Tourmaline-II, which crystallizes at a lower temperature, overgrowing tourmaline-I or occurring as isolated crystals, is distinguished by a higher Fe_tot/(Fe_tot + Mg), which varies from 0.46 to 0.72. The Fe_tot/(Fe_tot + Mg) ratio in tourmaline-III, which overgrows tourmaline-II is lower (0.35–0.49), and is identical to that of the first tourmaline generation. This is probably caused by the beginning of sulfide deposition. Tourmalines in the deposit characterized by complex isomorphic substitutions can be attributed to the intermediate members of the dravite—“hydroxy-uvite”-“oxy-uvite” and schorl-“hydroxy-feruvite”-“oxy-feruvite” series. Tourmaline starts to crystallize at temperatures above 340°C. The fluid responsible for the tourmaline deposition was magmatic, with a significant admixture of meteoric water (δ¹⁸O_{H 2}O = −0.85 to −0.75‰). The high Fe³⁺/Fe_tot ratio (0.50) indicates high oxygen activity when the tourmaline precipitated. It has been established that the isomorphic substitution Fe_tot → Al is typomorphic of tourmalines from porphyry copper deposits worldwide.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.