Tectonothermal evolution of the gneiss complex at Salur in the Eastern Ghats Grnaulite Belt of India

Textural relations, thermobarometry and petrogenetic grid considerations in the syn-tectonic granitoid massif and the enveloping metasedimentary gneisses at Salur are consistent with a counter-clockwise P–T –t path for the rocks. The low-P/high-T prograde sector is documented by the pre- to syn-D₁ cordierite±orthopyroxene±garnet±spinel–bearing metatexite leucosomes in metapelites. Heating and loading of the rocks (syn- to post-D₁) resulted in the formation of garnet+orthopyroxene± cordierite-bearing diatexites, and decomposition of cordierite in metatexite leucosomes to orthopyroxene+sillimanite+biotite+quartz symplectites. Near-peak temperature, 850 °C at 8.0 kbar, was reached syn- to post-D₂. Post-peak cooling resulted in the stabilization of coronal grossular and anorthite+calcite symplectites at the expense of scapolite+wollastonite+calcite assemblages in calc-silicate gneisses, and the resetting of cation exchange temperatures at 700–750 °C. Near-isothermal decompression at c. 700–750 °C is manifested by the decomposition of garnet porphyroblasts in the granitoid gneisses to plagioclase+orthopyroxene/ilmenite/biotite two-phase coronas and restabilization of cordierite at garnet margins in metapelites. Subsequent low-P, near-isobaric cooling led to the overprinting of granulite facies assemblages by muscovite+calcite assemblages, and further resetting of cation exchange thermometers to lower temperatures c. 600 °C. The tectonothermal evolution of the Salur gneiss complex vis-a-vis the Eastern Ghats Belt is therefore consistent with high degrees of lower crustal melting, followed by prograde heating of the cover rocks due to magma invasion synchronous with crustal compression, and finally thermal relaxation over a protracted period punctuated by tectonic/erosional denudation of the thickened crust.     

Fluid-rock history of granulite facies humite-marbles from Ambasamudram, southern India.

An extensive humite‐bearing marble horizon within a supracrustal sequence at Ambasamudram, southern India, was studied using petrological and stable isotopic techniques to define its metamorphic history and fluid characteristics. At peak metamorphic temperatures of 775±73°C, based on calcite‐graphite carbon isotope thermometry, the mineral assemblages suggest layer‐by‐layer control of fluid compositions. Clinohumite + calcite‐bearing assemblages suggest X_CO2 < 0.4 (at 700°C and 5 kbar), calcite + forsterite + K‐feldspar‐bearing assemblages suggest X_CO2>0.9 (at 790°C); and local wollastonite + scapolite + grossular‐bearing zones formed at X_CO2 of c. 0.3. Retrograde reaction textures such as scapolite + quartz symplectites after feldspar and calcite and replacement of dolomite + diopside or tremolite+dolomite after calcite+forsterite or calcite+clinohumite are indicative of retrogression under high X_CO2 conditions. Calcite preserves late Proterozoic carbon and oxygen isotopic signatures and the marble lacks evidence for extensive retrograde fluid infiltration, while during prograde metamorphism the possible infiltration of aqueous fluids did not produce significant isotopic resetting. Isotopic zonation of calcite and graphite grains was likely produced by localized CO₂ fluid infiltration during retrogression. Contrary to the widespread occurrence of humite‐marbles related to retrograde aqueous fluid infiltration, the Ambasamudram humite‐marbles record a prograde‐to‐peak metamorphic humite formation and retrogression under conditions of low X_H2O.     

In situ LA-(MC)-ICP-MS trace element and Nd isotopic compositions and genesis of polygenetic titanite from the Baogutu reduced porphyry Cu deposit,Western Junggar,NW China

Titanite (sphene, CaTiSiO₅) is sensitive to changes in temperature, oxygen and water fugacity, and fluid composition. In order to understand formation processes and the nature of hydrothermal fluids, various types of titanite from Cu ores at the Baogutu reduced porphyry Cu deposit were chosen for detailed study. Magmatic titanite is associated with biotite, plagioclase and K-feldspar, whereas hydrothermal titanite occurs with K-feldspar, chlorite, actinolite and calcite. The formation of hydrothermal titanite was related to hydration of igneous minerals under high fH₂O, whereas the widespread replacement of ilmenite by titanite (without magnetite) indicates a relatively low oxygen fugacity. Magmatic titanite has low Al, high Fe, Y, Sn, Zr, Nb and REE contents, relative to hydrothermal titanite. On the basis of the Zr-in-titanite and Al-in-chlorite geothermometers, formation temperatures for magmatic and hydrothermal titanite are estimated to be 687–739 °C and 250–670 °C, respectively. The gradual decrease in REE, Y and Sn contents from magmatic to late hydrothermal titanite was probably caused by precipitation of REE-bearing minerals. Magmatic and hydrothermal titanites have similar chondrite-normalized REE patterns with negative Eu anomalies and relatively flat HREE. Randomly selected titanites have Nd isotopic compositions similar to the host rocks. Thus, both magmatic and hydrothermal titanite are believed to have been predominantly derived from a mantle source.     

Skarn development from limestone adjacent to the Glenrock Granodiorite,Marulan Batholith,New South Wales,Australia

Skarns are developed over two temperature‐time intervals in calcite limestone adjacent to the southern extension of the Glenrock Granodiorite, a pluton of the Marulan Batholith, Southern Highlands, New South Wales. The initial volumetrically‐dominant prograde phase of skarn formation produced a suite comprising bimetasomatic skarn, including pyroxene endoskarn, potassic endoskarn and wollastonite‐bearing exoskarn, together with mineralogically‐zoned vein skarn, massive garnet‐pyroxene skarn and calcite‐vesuvianite skarn. Retrograde replacement is manifested by the development of hydrous silicate minerals, carbonate and cross‐cutting sulphide veinlets.

A genetic model is proposed to account for the development of bimetasomatic skarn in the deposit. Exoskarn geochemistry indicates addition of many components relative to an essentially pure limestone precursor, including Si, Al, Fe, Zr, Zn, S, Mn and Cu, negligible transfer of K, Na and Rb and loss of CO₂. Strontium and Ca loss from the parent limestone is indicated by mass balance calculations at constant volume.

Garnet and pyroxene compositions in the massive garnet‐pyroxene skarn range from Gr₃₀ to Gr₆₆ and Hd₆₁ to Hd₈₇, respectively. Compositions from Gr₆₇ to Gr₉₅ are typical of the vein skarn garnets. Chemical zonation patterns in garnet, pyroxene and vesuvianite are generally characterized by rim Fe depletion relative to cores of grains.

Prograde skarn probably formed at T = 500–580°C; P < 220 MPa. The massive garnet‐pyroxene skarn evolved under conditions of log fO₂ = ‐18.9 to ‐22.9 (assuming a constant fCO₂ of 20 MPa) within the fS₂ stability field of pyrrhotite. Retrograde skarn formed at T < 400°C, possibly under conditions of X_H2O < 0.01.

Vesuvianite plus wollastonite assemblages, present in exoskarn, probably attest to very water‐rich conditions. The marble wall rocks, isolated from the source of skarn‐forming fluids, probably evolved under conditions of minimum X_co2 >0.2. Low temperature CO₂ ‐rich fluid inclusions and prehnite (stable at X_co2 <0.01), present in the marble and skarn, respectively, suggest that substantial differences in X_co2: X_H2O were maintained during cooling.

Observed mineralogical and chemical zonation within the skarn reflects the complex interaction of T, P, fO₂, Xco₂ and other chemical variables such as a_SiO2 and a_Al2O3 throughout the skarn system. No single variable can account adequately for the mineralogical diversity observed in the skarn deposit.     

Malayaite and tin‐bearing silicates from a skarn at Doradilla via Bourke,New South Wales

An extensive complex zoned skarn is developed at the contact of a leucoadamellite intrusive at Doradilla, NW New South Wales. The skarn is a disequilibrium assemblage resulting from a progressive sequence of replacement of a carbonate precursor. Early grossular‐clinopyroxene rocks are replaced by andradite with 0.5–3.5 wt.% SnO₂ clinopyroxene and quartz. Later alteration along fractures and bedding planes of the garnet‐clinopyroxene quartz assemblage has produced calcite‐malayaite (CaSn0.95Ti0.05SiO₅) veins. The final replacement stage was the overprinting of the silicate phases by assemblages containing sulphides, cassiterite, magnetite, titanite, fluorite, biotite and chlorite. The tin content of garent increases with increasing andradite component suggesting replacement of Fe³⁺ by Sn⁴⁺. Associated clinopyroxenes contain 0.1% SnO₂. The coexistence of titanite and its tin isomorph malayaite with extremely limited solid solution indicates late stage skarn temperatures of less than 400°C.     

Fluid evolution of the Chalukou giant Mo deposit in the northern Great Xing'an Range,NE China

The Chalukou giant Mo deposit in the Heilongjiang Province, northeastern China, is a porphyry deposit hosted in an intermediate‐felsic complex surrounded by Mesozoic volcano–sedimentary rocks. The mineralization process is composed of four stages, including quartz + K‐feldspar (Stage I), quartz + molybdenite (Stage II), pyrite + chalcopyrite + quartz ± other sulphides (Stage III) and carbonate ± fluorite ± quartz (Stage IV). The mineralization is generally associated with intense K‐feldspar‐, fluorite‐, phyllic‐ and propylitic alteration. Primary fluid inclusions (FIs) in quartz include four compositional types, i.e. pure carbonic (PC‐type), aqueous‐carbonic (C‐type), daughter mineral‐bearing (S‐type) and aqueous (W‐type) inclusions. Halite, sylvite and hematite are recognized as the daughter minerals in Stage I S‐type FIs, whereas molybdenite and chalcopyrite occur as daughter minerals in Stage II S‐type FIs. High‐salinity and high pressure (>220 MPa) FIs exist in Stage I quartz veins, characterized by homogenization through halite dissolution at temperatures of 324 to 517 °C. The paucity of coexisting vapour‐rich FIs with similar homogenization temperatures at this stage indicates that the initial S‐type inclusions have directly exsolved from the magma rather than boiling off of a low‐salinity vapour. Stage I quartz has captured the C‐ and W‐type FIs, which have totally homogenized at 270–530 °C with salinities of 1.6–17.0 wt.% NaCl equiv. At Stage II, the coexistence of all FI types were only observed at pressures of 150–218 MPa and temperatures of 352–375 °C, with two salinity clusters of 0.9–16.6 wt.% NaCl equiv. and 37–56 wt.% NaCl equiv. Stage III quartz contains W‐type FIs with homogenization temperatures of 158–365 °C, salinities of 0.5–9.0 wt.% NaCl equiv., and minimum pressures of 12–116 MPa; whilst Stage IV fluorite or calcite only contains W‐type FIs with homogenization temperatures of 121–287 °C, salinities of 0.5–5.3 wt.% NaCl equiv., and minimum pressures of 10–98 MPa. The estimated trapping pressure from Stages II to III suggests an alternating lithostatic–hydrostatic fluid‐system caused by fluid boiling. Ore fluids at the Chalukou Mo deposit may have been evolved from a CO₂‐rich, high‐salinity, and high‐oxygen fugacity (fO₂) magma system, to a CO₂‐poor, low‐salinity, and low‐fO₂ epithermal system. Two key points may have contributed to the formation of the Chalukou giant Mo deposit: The magmatic origin and fluid boiling that has resulted in decompression and rapid precipitation of metals. Copyright © 2014 John Wiley & Sons, Ltd.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Phase-equilibrium constraints on titanite and rutile activities in mafic epidote amphibolites and geobarometry using titanite–rutile equilibria

Activities of titanite (Ttn, CaTiSiO₅) and/or rutile (Rt, TiO₂) phase components were calculated for 45 well‐characterized natural titanite‐ or rutile‐undersaturated epidote–amphibolites by using the equilibria: (i) 3 anorthite + 2 zoisite/clinozoisite + rutile + quartz = 3 anorthite + titanite + water (referred to as TZARS) and (ii) anorthite + 2 titanite = grossular + 2 rutile + quartz (referred to as GRATiS). In titanite‐bearing and rutile‐absent samples a_Rt is 0.75 ± 0.26. In titanite‐absent, rutile‐bearing samples a_Ttn is 0.89 ± 0.16. Mean values derived for a_Rt/a_Ttn are 0.92 ± 0.12 for rutile + titanite‐bearing samples and 0.42 ± 0.27 for samples lacking both titanite and rutile. Use of these values with TZARS yields pressure estimates for epidote–amphibolites that differ on average by <0.5 kbar from those recorded by established mineral barometers, even where both titanite and rutile are lacking. Despite rather large uncertainties in the average values obtained for a_Rt, a_Ttn or a_Rt/a_Ttn, application of TZARS yields pressure estimates that agree with independent estimates to within ±0.5 kbar for titanite‐ and/or rutile‐saturated samples, and to within ±0.8 kbar for samples that contain neither Ti‐phase. The accuracy and precision of the TZARS barometer are comparable to that of many well‐calibrated barometers. TZARS offers a much‐needed barometer for mafic rocks metamorphosed at epidote‐bearing amphibolite and blueschist facies conditions. In addition, the results provide a basis for application of other thermobarometers, such as Ti‐in‐zircon, where rutile activity is required as input.     

Humite- and scapolite-bearing assemblages in marbles and calcsilicates of Dronning Maud Land, Antarctica: new data for Gondwana reconstructions

This study investigates marbles and calcsilicates in Central Dronning Maud Land (CDML), East Antarctica. The paleogeographic positioning of CDML as part of Gondwana is still unclear; however, rock types, mineral assemblages, textures and P–T conditions observed in this study are remarkably similar to the Kerala Khondalite Belt in India. The CDML marbles and calcsilicates experienced a Pan-African granulite facies metamorphism at c. 570 Ma and an amphibolite facies retrogression at c. 520 Ma. The highest grade assemblage in marbles is forsterite+spinel+calcite+dolomite, in calcsilicates the assemblages are diopside+spinel, diopside+garnet, scapolite+wollastonite+clinopyroxene±quartz, scapolite±anorthite±calcite+clinopyroxene+wollastonite. These assemblages constrain the peak metamorphic conditions to 830±20 °C, 6.8±0.5 kbar and X _CO2>0.46. During retrogression, highly fluoric humite-group minerals (humite, clinohumite, chondrodite) replaced forsterite, and garnet rims formed at the expense of scapolite during reactions with wollastonite, calcite or clinopyroxene but without involvement of anorthite. Metamorphic conditions were about 650 °C, 4.5±0.7 kbar, 0.2< X _CO2^fluid<0.36, and the co-existence of garnet, clinopyroxene, wollastonite and quartz constrains f_O2 to FMQ-1.5 log units. Mineral textures indicate a very limited influx of H₂O-rich fluid during amphibolite facies retrogression and point to significant variations of fluid composition in mm-sized areas of the rock. Gypsum was observed in two samples; it probably replaced metamorphic anhydrite which appears to have formed under amphibolite facies conditions. The observed extensive anorogenic magmatism (anorthosites, A-type granitoids) and the character of metamorphism between 610 and 510 Ma suggest that the crustal thermal structure was characterized by a long-lived (50–100 Ma) rise of the crustal geotherm probably caused by magmatic underplating.     

Calcite–graphite isotope thermometry in amphibolite facies marble, Bancroft, Ontario

This study presents calcite–graphite carbon isotope fractionations for 32 samples from marble in the northern Elzevir terrane of the Central Metasedimentary Belt, Grenville Province, southern Ontario, Canada. These results are compared with temperatures calculated by calcite–dolomite thermometry (15 samples), garnet–biotite thermometry (four samples) and garnet–hornblende thermometry (three samples). Δ_cal‐gr values vary regularly across the area from >6.5‰ in the south to 4.0‰ in the north, which corresponds to temperatures of 525 °C in the south to 650 °C in the north. Previous empirical calibration of the calcite–graphite thermometer agrees very well with calcite–dolomite, garnet–biotite and garnet–hornblende thermometry, whereas, theoretical calibrations compare less well with the independent thermometry. Isograds in marble based on the reactions rutile + calcite + quartz =titanite and tremolite + calcite + quartz = diopside, span temperatures of 525–600 °C and are consistent with calculated temperature–X(CO₂) relations. Results of this study compare favourably with large‐scale regional isotherms, however, local variation is greater than that revealed by large‐scale sampling strategies. It remains unclear whether the temperature–Δ_cal‐gr relationship observed in natural materials below 650 °C represents equilibrium fractionations or not, but the regularity and consistency apparent in this study demonstrate its utility for thermometry in amphibolite facies marble.     

Characteristics of Triassic epithermal Au mineralization at the Q prospect,Chatree mining area,Central Thailand

The Chatree deposit is located in the Loei‐Phetchabun‐Nakhon Nayok volcanic belt that extends from Laos in the north through central and eastern Thailand into Cambodia. Gold‐bearing quartz veins at the Q prospect of the Chatree deposit are hosted within polymictic andesitic breccia and volcanic sedimentary breccia. The orebodies of the Chatree deposit consist of veins, veinlets and stockwork. Gold‐bearing quartz veins are composed mainly of quartz, calcite and illite with small amounts of adularia, chlorite and sulfide minerals. The gold‐bearing quartz veins were divided into five stages based on the cross‐cutting relationship and mineral assemblage. Intense gold mineralization occurred in Stages I and IV. The mineral assemblage of Stages I and IV is characterized by quartz–calcite–illite–laumontite–adularia–chlorite–sulfide minerals and electrum. Quartz textures of Stages I and IV are also characterized by microcrystalline and flamboyant textures, respectively. Coexistence of laumontite, illite and chlorite in the gold‐bearing quartz vein of Stage IV suggests that the gold‐bearing quartz veins were formed at approximately 200°C. The flamboyant and brecciated textures of the gold‐bearing quartz vein of Stage IV suggest that gold precipitated with silica minerals from a hydrothermal solution that was supersaturated by boiling. The δ¹⁸O values of quartz in Stages I to V range from +10.4 to +11.6‰ except for the δ¹⁸O value of quartz in Stage IV (+15.0‰). The increase in δ¹⁸O values of quartz at Stage IV is explained by boiling. P_H2O is estimated to be 16 bars at 200°C. The f_CO2 value is estimated to be 1 bar based on the presence of calcite in the mineral assemblage of Stage IV. The total pressure of the hydrothermal solution is approximately 20 bars at 200°C, suggesting that the gold‐bearing quartz veins of the Q prospect formed about 200 m below the paleosurface.     

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.     

A magmatic-hydrothermal transition in Arkaroola (northern Flinders Ranges, South Australia): from diopside–titanite pegmatites to hematite–quartz growth

A set of Palaeozoic diopside–titanite veins are present in Mesoproterozoic metagranites and metasediments that constitute the basement (Mt Painter Inlier) of the Adelaide Fold Belt (South Australia). These massive veins (up to 1 m) of pegmatitic nature contain large crystals of diopside, LREE–Y-enriched titanite (up to 40 cm in length) and minor amounts of quartz. They can be used to trace the system’s development from a high-temperature magmatic stage through to a massive hydrothermal event. The pegmatitic origin of these veins is evident from a complex fluid-melt inclusion assemblage, consisting of a highly saline inhomogeneous fluid and relicts of melt. Immiscibility of melt and heterogeneous highly saline fluids (exceeding 61 eq. mass% NaCl) is preserved in primary inclusions in diopside and secondary inclusions in titanite, indicating relatively shallow conditions of formation (510 ± 20°C and 130 ± 10 MPa). Graphic intergrowth of diopside and albite occurs at the contact with granitic pegmatites. The system evolved into hydrothermal conditions, which can be deduced from a later population of only fluid inclusions (homogeneous and less saline, ≈ 40 eq. mass% NaCl), trapped around 350 ± 20°C and 80 ± 10 MPa. During quartz crystallization, the conditions moved across the halite liquidus resulting in a heterogeneous mixture of brine and halite crystals, which were trapped at 200 ± 20°C and 50 ± 10 MPa. Brecciation and a palaeo-geothermal system overprinted the pegmatitic veins with an epithermal hematite–quartz assemblage and lesser amounts of bladed calcite and fluorite, in an intermittently boiling hydrothermal system of fairly pure H₂O at 100–140°C and 1–5 MPa. Remobilization of LREEs and Y from titanite and/or the granitic host rock is evidenced by precipitation of apatite, allanite and wakefieldite in an intermediate stage. Occasional incorporation of radioactive elements or minerals, presumably U-rich, in the fluorite is responsible for radiolysis of H₂O to H₂.     

A mineral equilibria study of the hydrothermal alteration in mafic greenschist facies rocks at Kalgoorlie, Western Australia

The influx of a H₂O–CO₂‐dominated fluid into actinolite‐bearing metabasic rocks during greenschist facies metamorphism in the Kalgoorlie area of Western Australia resulted in a zoned alteration halo around inferred fluid conduits that contain gold mineralisation. The alteration halo is divided into two outer zones, the chlorite zone and the carbonate zone, and an inner pyrite zone adjacent to the inferred fluid conduits. Reaction between the fluid and the protolith resulted in the breakdown of actinolite and the development of chlorite, dolomite, calcite and siderite. In addition, rocks in the pyrite zone developed muscovite‐bearing assemblages as a consequence of the introduction of potassium by the fluid. Mineral equilibria calculations undertaken using the computer software thermocalc in the model system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ show that mineral assemblages in the outer zones of the alteration halo are consistent with equilibrium of the protoliths with a fluid of composition X_CO2 = CO₂/(CO₂ + H₂O) = 0.1–0.25 for temperatures of 315–320 °C. The inner zone of the alteration halo reflect equilibrium with a fluid of composition X_CO2≈ 0.25. Fluid‐rock buffering calculations show that the alteration halo is consistent with interaction with a single fluid composition and that the zoned structure of the halo reflects the volume of this fluid with which the rocks reacted. This fluid is likely to have also been the one responsible for the gold mineralisation at Kalgoorlie.     

Association of Electrum and Calcite and Its Significance to the Genesis of the Hishikari Gold Deposits, Southern Kyushu, Japan

Abstract. Mineral assemblage, precipitation sequence and textures of the gold‐bearing veins from the Hishikari epithermal vein‐type deposits, southern Kyushu, Japan, were examined. In addition, fluid inclusion microthermometry and carbon and oxygen isotopic compositions of calcite were determined. Calcite, and that replaced by quartz, were commonly observed throughout the precipitation sequence of the veins. Thus, calcite must be a more common gangue constituent initially than observed presently. Association of calcite and electrum is observed immediately subsequent to columnar adularia in some vein samples. In addition, close association of electrum with pseudo‐acicular quartz, and electrum with truscottite were observed. The initial coprecipitation of electrum and calcite might be a common phenomenon in the gold‐bearing veins at the Hishikari deposits. The Th (homogenization temperature) data from the Honko‐Sanjin deposits are generally higher than those from the Yamada deposit. Samples that show association of calcite and electrum yielded higher Th (206–217°C, average) than the Th data from calcite associated with low‐grade Au ore or barren (180–204°C, average). The measured Tm (temperature of last melting point of ice) range from ‐0.4 to 0.0°C. The result suggests that the salinity of the hydrothermal solution was low during the precipitation both of calcite associated with Au mineralization and of barren calcite. Fluid inclusion evidence suggestive of boiling of hydrothermal solution for the precipitation of calcite was not recognized in the present work. The δ¹³C and δ¹⁸O values of calcite range from ‐10.8 to —4.7 % and from +3.2 to +15.2 %, respectively. The δ¹³C value of H₂CO₃ and the δ¹⁸O value of H₂O in the hydrothermal fluids calculated assuming isotopic equilibrium with calcite using the temperature obtained by fluid inclusion microthermometry, range from ‐14.4 to ‐9.1 %, and from ‐6.2 to +5.5 %, respectively. Thus, the calculated δ¹⁸O values of H₂O for calcite further confirm the presence of the ¹⁸O‐enriched ore fluids during the mineralization at the Hishikari deposits. The hydrothermal solution isotopically equilibrated with the sedimentary basement rocks was responsible for the gold mineralization associated with calcite.     

Epithermal Gold-Silver Mineralization of the Asachinskoe Deposit in South Kamchatka, Russia

The Asachinskoe epithermal Au‐Ag deposit is a representative low‐sulfidation type of deposit in Kamchatka, Russia. In the Asachinskoe deposit there are approximately 40 mineralized veins mainly hosted by dacite–andesite stock intrusions of Miocene–Pliocene age. The veins are emplaced in tensional cracks with a north orientation. Wall‐rock alteration at the bonanza level (170–200 m a.s.l.) consists of the mineral assemblage of quartz, pyrite, albite, illite and trace amounts of smectite. Mineralized veins are well banded with quartz, adularia and minor illite. Mineralization stages in the main zone are divided into stages I–IV. Stage I is relatively barren quartz–adularia association formed at 4.7 ± 0.2 Ma (K‐Ar age). Stage II consists of abundant illite, Cu‐bearing cryptomelane and other manganese oxides and hydroxides, electrum, argentite, quartz, adularia and minor rhodochrosite and calcite. Stage III, the main stage of gold mineralization (4.5–4.4 ± 0.1–3.1 ± 0.1 Ma, K‐Ar age), consists of a large amount of electrum, naumannite and Se‐bearing polybasite with quartz–adularia association. Stage IV is characterized by hydrothermal breccia, where electrum, tetrahedrite and secondary covellite occur with quartz, adularia and illite. The concentration of Au+Ag in ores has a positive correlation with the content of K₂O + Al₂O₃, which is controlled by the presence of adularia and minor illite, and both Hg and Au also have positive correlations with the light rare‐earth elements. Fluid inclusion studies indicate a salinity of 1.0–2.6 wt% NaCl equivalent for the whole deposit, and ore‐forming temperatures are estimated as approximately 160–190°C in stage III of the present 218 m a.s.l. and 170–180°C in stage IV of 200 m a.s.l. The depth of ore formation is estimated to be 90–400 m from the paleo‐water table for stage IV of 200 m a.s.l., if a hydrostatic condition is assumed. An increase of salinity (>C_NaCl≈ 0.2 wt%) and decrease of temperature (>T ≈ 30°C) within a 115‐m vertical interval for the ascending hydrothermal solution is calculated, which is interpreted as due to steam loss during fluid boiling. Ranges of selenium and sulfur fugacities are estimated to be logfSe2 = ?17 to ?14.5 and logfS2 = ?15 to ?12 for the ore‐forming solution that was responsible for Au‐Ag‐Se precipitation in stage III of 200 m a.s.l. Separation of Se from S‐Se complex in the solution and its partition into selenides could be due to a relatively oxidizing condition. The precipitation of Au‐Ag‐Se was caused by boiling in stage III, and the precipitation of Au‐Ag‐Cu was caused by sudden decompression and boiling in stage IV.     

Diffusion-controlled growth of wollastonite rims between quartz and calcite: comparison between nature and experiment

Growth rates of wollastonite reaction rims between quartz and calcite were experimentally determined at 0.1 and 1 GPa and temperatures from 850 to 1200 °C. Rim growth follows a parabolic rate law indicating that this reaction is diffusion‐controlled. From the rate constants, the D′δ‐values of the rate‐limiting species were derived, i.e. the product of grain boundary diffusion coefficient D′ and the effective grain boundary width, δ. In dry runs at 0.1 GPa, wollastonite grew exclusively on quartz surfaces. From volume considerations it is inferred that (D′_CaOδ)/(D′_SiO2δ)≥1.33, and that SiO₂ diffusion controls rim growth. D′_SiO2δ increases from about 10^?25 to 10^?23 m³ s^?1 as temperature increases from 850 to 1000 °C, yielding an apparent activation energy of 330±36 kJ mol^?1. In runs at 1 GPa, performed in a piston‐cylinder apparatus, there were always small amounts of water present. Here, wollastonite rims always overgrew calcite. Rims around calcite grains in quartz matrix are porous and their growth rates are controlled by a complex diffusion‐advection mechanism. Rim growth on matrix calcite around quartz grains is controlled by grain boundary diffusion, but it is not clear whether CaO or SiO₂ diffusion is rate‐limiting. D′δ increases from about 10^?21 to 10^?20 m³ s^?1 as temperature increases from 1100 to 1200 °C. D′_SiO2δ or D′_CaOδ in rims on calcite is c. 10 times larger than D′_SiO2δ in dry rims at the same temperature. Growth structures of the experimentally produced rims are very similar to contact‐metamorphic wollastonite rims between metachert bands and limestone in the Bufa del Diente aureole, Mexico, whereby noninfiltrated metacherts correspond to dry and brine‐infiltrated metacherts to water‐bearing experiments. However, the observed diffusivities were 4 to 5 orders of magnitude larger during contact‐metamorphism as compared to our experimental results.     

Formation of wollastonite-bearing marbles during late regional metamorphic channelled fluid flow in the Upper Calcsilicate Unit of the Reynolds Range Group,central Australia*

Abstract Granulite facies marbles from the Upper Calcsilicate Unit of the Reynolds Range, central Australia, contain metre-scale wollastonite-bearing layers formed by infiltration of water-rich (X_CO2= 0.1–0.3) fluids close to the peak of regional metamorphism at c. 700° C. Within the wollastonite marbles, zones that contain <10% wollastonite alternate on a millimetre scale with zones containing up to 66% wollastonite. Adjacent wollastonite-free marbles contain up to 11% quartz that is uniformly distributed. This suggests that, although some wollastonite formed by the reaction calcite + quartz = wollastonite + CO₂, the wollastonite-rich zones also underwent silica metasomatism. Time-integrated fluid fluxes required to cause silica metasomatism are one to two orders of magnitude higher than those required to hydrate the rocks, implying that time-integrated fluid fluxes varied markedly on a millimetre scale. Interlayered millimetre -to centimetre-thick marls within the wollastonite marbles contain calcite + quartz without wollastonite. These marls were probably not infiltrated by significant volumes of water-rich fluids, providing further evidence of local fluid channelling. Zones dominated by grandite garnet at the margins of the marl layers and marbles in the wollastonite-bearing rocks probably formed by Fe metasomatism, and may record even higher fluid fluxes. The fluid flow also reset stable isotope ratios. The wollastonite marbles have average calcite (Cc) δ¹⁸O values of 15.4 ± 1.6% that are lower than the average δ¹⁸O(Cc) value of wollastonite-free marbles (c. 17.2 ± 1.2%). δ¹³C(Cc) values for the wollastonite marbles vary from 0.4% to as low as -5.3%, and correlations between δ¹⁸O(Cc) and δ¹³C(Cc) values probably result from the combination of fluid infiltration and devolatilization. Fluids were probably derived from aluminous pegmatites, and the pattern of mineralogical and stable isotope resetting implies that fluid flow was largely parallel to strike.     

Intragrain oxygen isotope zoning in titanite by SIMS: Cooling rates and fluid infiltration along the Carthage‐Colton Mylonite Zone,Adirondack Mountains,NY, USA

Oxygen isotopes are an attractive target for zoning studies because of the ubiquity of oxygen‐bearing minerals and the dependence of mineral ¹⁸O/¹⁶O ratios on temperature and fluid composition. In this study, subtle intragrain oxygen isotope zoning in titanite is resolved at the 10‐μm scale by secondary ion mass spectrometry. The patterns of δ¹⁸O zoning differ depending on microstructural context of individual grains and reflect multiple processes, including diffusive oxygen exchange, partial recrystallization, grain‐size reduction, and grain growth. Using the chronological framework provided by structural relations, these processes can be related to specific events during the Grenville orogeny. Titanite was sampled from two outcrops within the Carthage‐Colton Mylonite Zone (CCMZ), a long‐lived shear zone that ultimately accommodated exhumation of the Adirondack Highlands from beneath the Adirondack Lowlands during the Ottawan phase (1090–1020 Ma) of the Grenville orogeny. Titanite is hosted in the Diana metasyenite complex, which preserves three sequentially developed fabrics: an early NW‐dipping protomylonitic fabric (S₁) is crosscut by near‐vertical ultramylonitic shear zones (S₂), which are locally reoriented by a NNW‐dipping mylonitic fabric (S₃). Texturally early titanite (pre‐S₂) shows diffusion‐dominated δ¹⁸O zoning that records cooling from peak Ottawan, granulite‐facies conditions. Numerical diffusion models in the program Fast Grain Boundary yield good fits to observed δ¹⁸O profiles for cooling rates of 50 ± 20 °C Ma^?1, which are considerably faster than the 1–5 °C Ma^?1 cooling rates previously inferred for the Adirondack Highlands from regional thermochronology. High cooling rates are consistent with an episode of rapid shearing and exhumation along the CCMZ during gravitational collapse of the Ottawan orogen at c. 1050 Ma. Texturally later titanite (syn‐S₂) has higher overall δ¹⁸O and shows a transition from diffusion‐dominated to recrystallization‐dominated δ¹⁸O zoning, indicating infiltration of elevated‐δ¹⁸O fluids along S₂ shear zones and continued shearing below the blocking temperature for oxygen (~≤500 °C for grain sizes at the study site). The texturally latest titanite (post‐S₃) has growth‐dominated δ¹⁸O zoning, consistent with porphyroblastic grain growth following cessation of shearing along the Harrisville segment of the CCMZ.     

Ore Genesis and Tectonic Significance of the Xiaojiashan Tungsten Deposit,Eastern Tianshan,Xinjiang, China: Evidence from Geology,Fluid Inclusions,and Stable Isotope Geochemistry

The Xiaojiashan tungsten deposit is located about 200 km northwest of Hami City, the Eastern Tianshan orogenic belt, Xinjiang, northwestern China, and is a quartz vein‐type tungsten deposit. Combined fluid inclusion microthermometry, host rock geochemistry, and H–O isotopic compositions are used to constrain the ore genesis and tectonic setting of the Xiaojiashan tungsten deposit. The orebodies occur in granite intrusions adjacent to the metamorphic crystal tuff, which consists of the second lithological section of the first Sub‐Formation of the Dananhu Formation (D₂d ₁²). Biotite granite is the most widely distributed intrusive bodies in the Xiaojiashan tungsten deposit. Altered diorite and metamorphic crystal tuff are the main surrounding rocks. The granite belongs to peraluminous A‐type granite with high potassic calc‐alkaline series, and all rocks show light Rare Earth Element (REE)‐enriched patterns. The trace element characters suggest that crystallization differentiation might even occur in the diagenetic process. The granite belongs to postcollisional extension granite, and the rocks formed in an extensional tectonic environment, which might result from magma activity in such an extensional tectonic environment. Tungsten‐bearing quartz veins are divided into gray quartz vein and white quartz veins. Based on petrography observation, fluid inclusions in both kinds of vein quartz are mainly aqueous inclusions. Microthermometry shows that gray quartz veins have 143–354°C of T_h, and white quartz veins have 154–312°C of T_h. The laser‐Raman test shows that CO₂ is found in fluid inclusions of the tungsten‐bearing quartz veins. Quadrupole mass spectrometry reveals that fluid inclusions contain major vapor‐phase contents of CO₂, H₂O. Meanwhile, fluid inclusions contain major liquid‐phase contents of Cl^?, Na⁺. It can be speculated that the ore‐forming fluid of the Xiaojiashan tungsten deposit is characterized by an H₂O–CO₂, low salinity, and H₂O–CO₂–NaCl system. The range of hydrogen and oxygen isotope compositions indicated that the ore‐forming fluids of the tungsten deposit were mainly magmatic water. The ore‐forming age of the Xiaojiashan deposit should to be ~227 Ma. During the ore‐forming process, the magmatic water had separated from magmatic intrusions, and the ore‐bearing complex was taken to a portion where tungsten‐bearing ores could be mineralized. The magmatic fluid was mixed by meteoric water in the late stage.