Origin and evolution of hydrothermal fluids in epithermal Pb-Zn-Cu ± Au ± Ag deposits at Koru and Tesbihdere mining districts, Çanakkale,Biga Peninsula,NW Turkey

The Koru and Tesbihdere mining districts in Biga Peninsula, Northwestern Turkey, consist of twelve deposits covering approximately 12 km². The epithermal Au-Ag enriched base metal veins and associated low-grade breccia and stockwork at Koru and Tesbihdere are hosted by Oligocene subaerial and calc-alkaline volcanic rocks including basaltic andesite lavas, dacitic lava-tuffs, rhyolitic lava-domes and tuffs. NW- to N-trending strike-slip faults and E- and NE-trending faults constitute the most important ore-controlling structures in the Koru and Tesbihdere districts respectively. In the Koru mining district, galena is the dominant ore mineral in barite-quartz veins containing sphalerite, chalcopyrite, pyrite, bornite, enargite and tennantite. According to base metal content, the Tesbihdere mining district can be subdivided into sphalerite-galena dominated Tesbihdere mineralization and chalcopyrite-pyrite dominated Bakır and Kuyu Zones mineralization. Gold is present in small quantities with maximum 3.14 g/t Au values either as free grains in quartz or as micro inclusions in pyrite and galena. The most widespread silver minerals are polybasite, pearceite, argentite and native silver which commonly occur as replacements of galena, sphalerite and pyrite, and other sulfides, or as fillings of microfractures in sulfides and quartz.Microthermometric measurements of primary liquid-rich fluid inclusions in sphalerite, barite and quartz in Koru indicate that the veins were formed at temperatures between 407 and 146 °C from fluids with salinities between 0.7 and 12.5 wt.% equiv. NaCl. Barite from the Tahtalıkuyu, Kuyutaşı and 5^th Viraj mineralization show the highest homogenization temperatures. Fluid inclusion data for ore-stage quartz and sphalerite from the Tesbihdere mining district, indicate that these minerals were deposited at temperatures between 387 and 232 °C from more diluted fluids with moderate salinities between 0.2 and 10.6 wt.% NaCl equiv. Tahtalıkuyu and 5^th Viraj mineralization show only boiling trends while Kuyutaşı, Tesbihdere, Bakır and Kuyu Zones mineralization show both boiling and isothermal mixing trends. The O and H isotope compositions of ore fluids from the Tahtalıkuyu (δ¹⁸O = − 1.40 to 0.25‰; δD = − 72.49 to − 52.68‰) and Kuyutaşı (δ¹⁸O = − 2.29 to 3.59‰; δD = − 90.70 to − 70.93‰) mineralization indicate that there was a major contribution from a magmatic component to ore genesis. Based on 9 quartz samples associated with orebodies at the Tesbihdere mining district, the relatively higher δ¹⁸O and lower δD isotope compositions from hydrothermal fluids could be attributed to a relatively dilute fluid derived by the mixing with meteoric water. The Pb isotope compositions also reveal that most of the lead in both mining districts is derived from the Oligocene-Miocene magmatic rocks, possibly with smaller contributions from the Eocene magmatic rocks.     

The optimal windows for seismically-enhanced gold precipitation in the epithermal environment

Epithermal gold (Au) deposits result from the combination of a sustained flux of metal-rich fluids and an efficient precipitation mechanism. Earthquakes may trigger gold precipitation by rapid loss of fluid pressure but their efficiency and time-integrated contribution to gold endowment are poorly constrained. In order to quantify the feedbacks between earthquake-driven fracturing and gold precipitation in the shallow crust, we studied the gold-rich fluids in the active Tolhuaca geothermal system, located in the highly seismic Southern Andes of Chile. We combined temperature measurements in the deep wells with fluid inclusion data, geochemical analyses of borehole fluids and numerical simulations of coupled heat and fluid flow to reconstruct the physical and chemical evolution of the hydrothermal reservoir. The effect of seismic perturbations on fluid parameters was constrained using a thermo-mechanical piston model that simulates the suction pump mechanism occurring in dilational jogs. Furthermore, we evaluated the impact of fluid parameters on gold precipitation by calculating the solubility of gold in pressure (P)–enthalpy (H) space. The reconstructed fluid conditions at Tolhuaca indicate that single-phase convective fluids feeding the hydrothermal reservoir reach the two-phase boundary with a high gold budget (~ 1–5 ppb) at saturated liquid pressures between 20 and 100 bar (210 °C < T_sat < 310 °C). We show that if hydrothermal fluids reach this optimal threshold for gold precipitation at a temperature near 250 °C, small adiabatic pressure drops (~ 10 bar) triggered by transient fault-rupture can produce precipitation of 95% of the dissolved gold. Our results at the active Tolhuaca geothermal system indicate that subtle, externally-forced perturbations – equivalent to low magnitude earthquakes (Mw < 2) of a hydrothermal reservoir under optimal conditions – may significantly enhance gold precipitation rates in the shallow crust and lead to overall increases in metal endowment over time.     

The Mokrsko-West gold deposit,Bohemian Massif,Czech Republic: Mineralogy,deposit setting and classification

The Mokrsko-West deposit is unique among European Variscan gold deposits from the points of view of both the structure (an approx. 200 m thick complex of sheeted, several mm-thick, densely spaced quartz veins) and the economic viability (gold reserves of about 100 t). The deposit is hosted mainly by tonalite of the calc-alkaline Sázava tonalite suite (ca. 354 Ma) of the Central Bohemian Plutonic Complex. Mineralization is characterized by quartz-dominated gangue, no visible hydrothermal alteration, low sulfide content, high fineness native gold accompanied by maldonite, aurostibite, native bismuth and numerous Bi–Te–(S) phases. Five mineralogical stages are described in great detail. Arsenopyrite and chlorite thermometers, mineral phase stabilities and published isotope and fluid inclusion data are used to reconstruct the temperature and compositional evolution of the system. The role of liquid bismuth in the sequestration of gold is also discussed.The deposit shares the features of both orogenic gold (ORG) and intrusion-related gold (IRG) deposits. The IRG model is advocated by close spatial association between the ore zone and the tonalite host-intrusion, by the absence/scarcity of hydrothermal alteration, by the Au–Bi–Te–As elemental association and by marked thermal gradients from the early to late mineralization stages. The ORG model is advocated by an approx. 15–10 Ma gap between the intrusion of the tonalite-host and the ore formation, by isotope and geochemical evidence for a key role of metamorphic fluids in the mobilization and transfer of many elements/species (inclusive S and Au). The apparently ambiguous classification of the deposit can most probably be attributed to deposit formation at a depth of ≥ 9 km and to setting of the deposit at/inside a large-scale plutonic complex with multiple and prolonged tectonic and intrusive activity.     

Host rock characteristics and source of chromium and beryllium for emerald mineralization in the ophiolitic rocks of the Indus Suture Zone in Swat,NW Pakistan

Bodies of magnesite-rich rocks (magnesite ± talc ± quartz ± dolomite), locally containing emerald deposits, occur within the Swat Valley. These rocks, part of the Indus suture mélange group, are distributed mostly along contacts of serpentinized ultramafic rocks with carbonate ± graphite-bearing metasedimentary rocks. Their field association, petrographic details, mineralogical composition and geochemical characteristics show that they likely formed due to carbonate alteration of previously serpentinized ultramafic rocks by CO₂-bearing fluids released as a result of metamorphism of spatially associated, originally sedimentary rocks of the Indo-Pakistan plate.Locally, late-stage hydrothermal activity affected these highly fissile magnesite-rich rocks to produce veins and stockworks of quartz as well as emerald, Cr-rich tourmaline and Cr, Ni-rich muscovite. Detailed petrographic and mineral chemical investigations suggest that all three Cr-bearing silicates are genetically related and their Cr, as well as Ni and Mg found in Cr-rich muscovite and Cr-rich tourmaline, was derived from the original ultramafic protoliths.Detailed geochemical comparison reveals that relative to non-mineralized sections, magnesite-rich rocks in mineralized zones show significant enrichment in B and Be as well as As, Pb, Zr, Rb, Ba, W, Sn, Sr and Y. Boron and Be enrichment in these rocks appears to be structurally controlled. More extreme B and Be enrichment is evident in small granitic dikes cutting granite gneisses and in Miocene leucogranitic stocks at Malakand 45 km southwest. These geochemical features argue strongly for a leucogranite-associated source for Be-transporting fluids to the emerald's host rocks.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

Mineralogical and geochemical characteristics of the hydrothermal illite from Hoam granite,South Korea: Implications for episodic fluid injections in the hydrothermal alteration system

Two stages of illite mineralization are recognized in the hydrothermal alteration zone of the Hoam granite. These illites are formed as a result of pervasive alteration by re-equilibration with high water/rock in a brittle environment below <2 km; the mineralization timing is middle Oligocene (26–27 Ma), coinciding with the timing of crustal deformation related to the opening of the East Sea (Sea of Japan). The mineralogical and geochemical characteristics of the clearly distinguished illites at each site indicate that they were mineralized from different fluid injections in distinct geological environments. Illites at the site-1 alteration zone are characterized by high-K content [K_0.84 per O₁₀(OH)₂], 2M₁ polytype of 99 %, hexagonal plate shape, and coexistence with pyrite. These observations indicate that the illites were formed in a slow cooling system (>250 °C), high fS₂, and a relatively acidic environment. The pseudomorphic replacement combined with matrix-filling texture indicates that the illites at the site-1 alteration zone recorded the changes in fluid conditions from low to high water-rock ratio. In contrast, the illites at the site-2 alteration zone show the coexistence of polytypes (2M₁, 1M, and 1M_d), high-K illites [(K_0.83 per O₁₀(OH)₂]/low-K illites [K_0.63 per O₁₀(OH)₂], platy/hairy shapes, and presence of magnetite. Furthermore, this alteration zone no longer exhibits primary textures because of pervasive alteration induced by the dissolution-precipitation process. These results indicate that they were formed in a rapid cooling system and were continuously under conditions of high water-rock ratio, as well as in a less acidic and fS₂ environment than that observed at the site-1 alteration zone. The behavior of trace elements for each illite primarily depends on the constituents of the hydrothermal fluid, which reflect different degrees of fluid evolution. The enrichment of high field strength elements (Nb and Ta), large ion lithophile elements (B, Be, and Cs), rare earth elements, and actinide elements (U and Th) in illite at the site-2 alteration zone shows that these elements formed by a more evolved fluid than that of the illite at the site-1 alteration zone. In addition, negative Ce anomalies at the site-2 alteration zone indicate that these crystallized in a reducing environment. Considering the mineralogical and geochemical properties of illites at the site-1 and site-2 alteration zones, the illite mineralization in the Hoam granite was likely generated by at least two episodes of hydrothermal illite mineralization, which originated from episodic injections of fluids, rather than continuously evolved fluids.     

Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope,PGE, trace element,and REE geochemistry

The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ^98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ^98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 10⁷ compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.     

Multiple fluid sources/pathways and severe thermal gradients during formation of the Jílové orogenic gold deposit,Bohemian Massif,Czech Republic

The Jílové deposit in the central part of the Bohemian Massif represents a vein to stockwork type of orogenic-type gold deposit. It is hosted by Neoproterozoic rocks of the Jílové Belt and by various magmatic dikes related to the ~ 355 to ~ 335 Ma Central Bohemian Plutonic Complex. The deposit is situated along the terrane boundary of the Teplá Barrandian and Moldanubian units.The deposit offered an exceptional opportunity to trace O, C, S and Sr stable isotope evolution of parent fluids based on combined mineralogical and geochemical study of carbonate, quartz, scheelite, and sulfide minerals, which represent six stages of mineralization, including the gold-bearing event.Stable isotope data and mineral and isotope thermometry indicate gangue and ore mineral formation between ~ 350 °C and < 100 °C, which can be divided into 6 stages. Scheelite-bearing assemblages (stages 2–3) precipitated at 292 ± 8 °C from a fluid with calculated values: δ¹⁸O_SMOW = + 4.2 ± 0.5‰ and δ¹³C_PDB = − 11 ± 1‰. Gold precipitation (stage 5) probably started at about 300 °C, but the major event probably occurred at 230 ± 30 °C from a fluid with more variable isotope values (δ¹⁸O_SMOW = + 2.5 to + 5‰ and δ¹³C_PDB = − 9 to − 13.5‰). The carbon speciation was characterized by predomination of dissolved CO₂ (H₂CO_3ap.) in the fluids. Some gold, however, undoubtedly precipitated from bicarbonate dominated fluids even at < 120 °C.Extreme variations in the δ¹⁸O values of carbonate minerals, obtained from sampling profiles across individual veins with macroscopic gold, revealed severe thermal gradients during vein formation (~ 50 to ~ 100 °C difference of crystallization temperatures between the vein margin and core).The sulfur stable isotope composition of sulfide minerals indicates the dominant role of sulfur remobilization from Neoproterozoic rocks and stratiform mineralizations of the Jílové Belt by Variscan hydrothermal fluids. Similarly, the Sr-isotope composition of carbonates indicates both relatively primitive (⁸⁷Sr/⁸⁶Sr = 0.7055) and more evolved (⁸⁷Sr/⁸⁶Sr ~ 0.7090) fluid compositions, probably indicating fluid exchange with the Jílové Belt and the Central Bohemian Plutonic Complex rocks, respectively.Age determination of hydrothermal muscovite (related to stage 2) via ⁴⁰Ar/³⁹Ar indicated an age of 339.0 ± 1.5 Ma for the quartz veins. The mineralization is essentially coeval with the late intrusive phases of the Central Bohemian Plutonic Complex (i.e. the ultrapotassic suite) and with late-orogenic large-scale tectonic movements at the boundary between the two crustal terranes (Teplá-Barrandian and Moldanubian).Based on evaluation of the available age data on the hydrothermal and magmatic activity within the broader area of the Central Bohemian Plutonic Complex, we suggest two intervals of gold mineralization: 347 to 341 Ma and 340 to 337 Ma. The former interval overlaps with the intrusive activity of the Blatná high-K suite (granodiorite). The associated gold deposits (Mokrsko and Petráčkova hora) exhibit strong affiliation to the intrusion-related-gold-type deposit. The later interval overlaps with the ultrapotassic magmatism and is associated with more or less “classical” orogenic-gold-type deposits (Jílové, Bělčice, Libčice deposits).     

Physico-chemical controls on ore deposition in the Arapucandere Pb–Zn–Cu-precious metal deposit,Biga Peninsula,NW Turkey

Arapucandere is one of a number of similar Cu–Zn–Pb ± Au–Ag epithermal deposits in the Biga Peninsula, which are mineralogically and tectonically similar. Fluid inclusions have very low salinities between 1.7 and 0 wt.% NaCl and a wide range of temperatures from ~ 360 to 160 °C. There was extensive boiling and “flashing” of the hydrothermal fluids which initiated mineral deposition. The range of temperatures is consistent with emplacement of the veins at ~ 700 m depth, with the pressure decreasing from near lithostatic to near hydrostatic and a decrease in temperature to ~ 250 °C due to adiabatic expansion of the fluids. There is evidence of a limited amount of boiling, but the temperature and pressure decrease was close to the liquid–vapour curve. Flashing of the fluids was caused by sudden drops to sub-hydrostatic pressures and even lower temperatures. Mineralization was caused by these pressure related temperature decreases as there is no evidence of cooling and dilution of the ore-fluids. δ³⁴S values of sulphides indicate a magmatic source but the more negative than usual values also suggest boiling affected isotopes. δD and δ¹⁸O of the fluids indicate a mixing between meteoric waters and magmatic fluids, with the large range of δD due to boiling. LA-ICP-MS analyses of fluid inclusions reveal high Cu–Zn–Pb concentrations in the fluids, despite their low salinity, transported as chloride complexes. Exceptional pressure and temperature decrease causing the fluids to “flash” was likely to have been in response to earthquakes.     

Jurassic microbial communities in hydrothermal manganese crust of the Rifian Calcareous Chain,Northern Morocco

The stratigraphic record of the Middle and Upper Jurassic in the Western Tethys is characterized by successive eustatic and tectonic events recorded as stratigraphic unconformities, which are revealed by hardgrounds, palaeokarsts, palaeosoils, and by the deposition of Fe–Mn crusts. The study of a Mn crust from the Middle-Upper Jurassic discontinuity in the Jbel Moussa Group (Rifian Cordillera), from stratigraphic, geomicrobiologic, mineralogical, and geochemical standpoints allows us to establish its hydrothermal origin. The manganese crust is composed by Ca-birnessite, cryptomelane and coronadite. Major- and trace-elements analyses of the whole crust show high contents in MnO (> 70 wt.%), a negative Ce anomaly and a positive Eu anomaly. Analysis of the microstructures under scanning electron microscopy reveals crystalline and microbial laminations, probably owing to fungal mycelium. Mineralogical and geochemical composition, together with microbial structures, suggest that this Mn crust formed as a result of venting hydrothermal fluids through synsedimentary faults. Chemosynthetic microbes were probably involved in the precipitation of Mn.     

The Cu isotopic signature of granites from the Lachlan Fold Belt,SE Australia

This contribution reports our preliminary work to determine Cu isotope ratios for various granite rocks and examine the Cu isotope systematics within granite suites. A chemical procedure, modified from Maréchal [Maréchal, C.N., Télouk, P. and Albarède, F., 1999. Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chemical Geology, 156(1–4): 251–273.], was used to separate Cu from rock matrix. Quantitative recovery (100.6 ± 1.6%), with a low total procedural blank (2.65 ± 0.66 ng) for Cu, has been achieved, allowing Cu isotopic measurements on samples with as little as 10 ppm Cu. The Cu isotope ratios (δ⁶⁵Cu relative to NIST SRM 976) of 32 rock samples, ranging from mafic to felsic compositions, from 3 batholiths (2 I-type, 1 S-type) from the Lachlan Fold Belt in southeastern Australia, vary from ? 0.46‰ to 1.51‰. Most of them cluster around zero, with mean values for the I-type and S-type granites of 0.03 ± 0.15‰ and ? 0.03 ± 0.42‰ (2 sigma) respectively. These data, together with Cu isotope ratios of two loess samples, provide preliminary evidence that the baseline Cu isotopic composition of the crystalline part of upper continental crust is close to zero. The tight clustering of Cu isotope ratios of rocks from the I-type suites suggests that high-temperature magmatic processes do not produce significant Cu isotope fractionation. However, two granites with abnormally heavy Cu isotope signatures (up to 1.51‰) appears to be the result of localized hydrothermal alteration. Measurable variation in Cu isotopic composition of the S-type granite may reflect isotopic heterogeneity in the sedimentary source region as a result of redox processes or may be due to hydrothermal overprinting. Thus, Cu isotope geochemistry may be a useful tracer for studying hydrothermal alteration and source heterogeneity of granitic rocks.     

Massive sulfides of Mount Jourdanne along the super-slow spreading Southwest Indian Ridge and their genesis

Modern massive sulfide deposits are known to occur in diverse tectonic settings and it is generally expected that hydrothermal deposits of similar geological settings shall have more or less similar mineralogical and geochemical signatures. However, the Mount Jourdanne sulfide deposits along the super-slow spreading Southwest Indian Ridge deviate from this common concept. These sulfide precipitates are Zn-rich (up to 35 wt.%) and are characterized by high concentrations of Pb (≤ 3.5 wt.%), As (≤ 1.1 wt.%), Ag (≤ 0.12 wt.%), Au (≤ 11 ppm), Sb (≤ 967 ppm), and Cd (≤ 0.2 wt.%) which are unusual for a modern sediment-free mid-oceanic ridge system. Therefore, we have reinvestigated the sulfide samples collected during the INDOYO cruise in 1998, in order to explain their unusual mineralogy and geochemical composition. The sulfide samples are polymetallic and are classified as: a) chimneys, b) mounds, and c) hydrothermal breccias. The chimneys are small tube-like symmetrical bodies (30–40 cm high; ~ 10 cm diameter) and consist mainly of sphalerite and less chalcopyrite, set in a matrix of late amorphous silica. The inner wall shows a late-stage colloform sphalerite containing co-precipitates of galena and/or Pb–As sulfosalts. In contrast, the mound samples are dominated either by Fe-sulfides (pyrite) or by a mixture of pyrite and chalcopyrite with less sphalerite, pyrrhotite, amorphous silica and barite. Both, the chimney and mound samples, are characterized by layering and mineral zonation. The hydrothermal breccias are highly altered and mineralogically heterogeneous. They consist of silicified basaltic material that are impregnated with sulfides and contain cm-sized chimney fragments within a matrix of low-temperature minerals such as sphalerite and pyrite. The latter fragments mainly consist of chalcopyrite with isocubanite lamellae. In addition, these breccias contain late-stage realgar, boulangerite, galena, Pb–As sulfosalts and barite that are mostly confined to vugs or fractures. At least five mineralogical associations are distinguished that indicate different thermal episodes ranging from black smoker mineralization conditions to cessation of the hydrothermal activity. Based on the mineralogical associations and established literature in this regard, it is inferred that the mineralization at Mt. Jourdanne occurred mainly in three temperature domains. Above 300 °C, the chalcopyrite (with isocubanite)–pyrrhotite association formed whereas the sphalerite dominated assemblage with much less chalcopyrite and pyrite formed around and below 300 °C. The late-stage mineralization (below 200 °C) contains colloform sphalerite, galena, Pb–As sulfosalts, realgar and barite. The unusual mineralogy and trace element chemistry for this modern VHMS deposit could be explained assuming hydrothermal leaching of some felsic differentiates underneath the basaltic cover and subsequent zone refining processes.     

Geology,mineralogy, and geochemistry of fault-controlled hydrothermal Cu–Au mineralization in the Shanmen Volcanic Basin,SE China

The Yukeng–Banling deposit is a typical fault-controlled hydrothermal Cu–Au deposit in the Shanmen Volcanic Basin (SVB), SE China. Ore bodies commonly occur as lodes, lenses and disconnected pods dipping SW with vertical zonation of ore minerals. Ore-related hydrothermal alteration is well developed on both sides of the veins, dominated by silicification, sericitization, chloritization and argillation with a banded alteration zonation. The mineralization can be divided into three stages (stages I, II and III). Native gold is present as veinlets in fractures of fine-grained pyrite from stage II.Zircon U–Pb and Rb–Sr isochron ages indicate that the Cu–Au mineralization is coeval with the Caomen alkaline granite and Xiaokeng quartz-diorite, both emplaced at ca. 102 Ma. Microthermometric measurements of fluid inclusions in quartz and sphalerite from stage II veins indicate that the Yukeng–Banling deposit is an epithermal deposit. Six ore-related quartz grains have δD_H2O values of − 69 to − 43‰, and δ¹⁸O_H2O values calculated using total homogenization temperatures that range from − 2.0 to 0.7‰. All samples plot in an area between the magmatic field and the meteoric line, suggesting that the ore-forming fluids are derived from a mixed source of magmatic and meteoric waters. δ³⁴S values for eight pyrite separates range from − 2.1 to + 4.1‰ with an average of + 1.7‰, and δ³⁴S values for galena and sphalerite are 2.3‰ and 2.2‰, similar to magmatic sulfur. Four alkaline granite samples have Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb)_t = 18.175–18.411, (²⁰⁷Pb/²⁰⁴Pb)_t = 15.652–15.672 and (²⁰⁸Pb/²⁰⁴Pb)_t = 38.343–38.800. Three quartz-diorite samples have ratios (²⁰⁶Pb/²⁰⁴Pb)_t, (²⁰⁷Pb/²⁰⁴Pb)_t and (²⁰⁸Pb/²⁰⁴Pb)_t of 18.277–18.451, 15.654–15.693 and 38.673–38.846, respectively. These age-calculated lead isotopic data for alkaline granite are similar to those for the analyzed sulfides. Co/Ni ratios for stage II pyrites range from 1.42 to 5.10, indicating that the Yukeng–Banling deposit records the past involvement of magmatic hydrothermal fluids. The isotope data, together with geological, mineralogical and geochronological evidence, favor a primary magmatic source for sulfur and metals in the ore fluids. Mixing of the Cu- and Au-rich fluids with meteoric water led to precipitation of the Cu–Au veins along NW-trending faults.The Yukeng–Banling deposit, the contemporaneous Caomen alkaline granite and Xiaokeng quartz-diorite in the SVB formed under an extensional setting, due to high-angle subduction of the paleo-Pacific plate. The extensional setting facilitated the formation of Cu- and Au-rich magmas which was derived from enriched mantle and lower crust.     

Evidence of Mid-ocean ridge and shallow subduction forearc magmatism in the Nagaland-Manipur ophiolites,northeast India: constraints from mineralogy and geochemistry of gabbros and associated mafic dykes

We discuss here the mineralogical and geochemical characteristics of mafic intrusive rocks from the Nagaland-Manipur Ophiolites (NMO) of Indo-Myanmar Orogenic Belt, northeast India to define their mantle source and tectonic environment. Mafic intrusive sequence in the NMO is characterized by hornblende-free (type-I) and hornblende-bearing (type-II) rocks. The type-I is further categorized as mafic dykes (type-Ia) of tholeiitic N-MORB composition, having TiO₂ (0.72–1.93 wt.%) and flat REE patterns (La_N/Yb_N = 0.76–1.51) and as massive gabbros (type-Ib) that show alkaline E-MORB affinity, having moderate to high Ti content (TiO₂ = 1.18 to 1.45 wt.%) with strong LREE-HREE fractionations (La_N/Yb_N = 4.54–7.47). Such geochemical enrichment from N-MORB to E-MORB composition indicates mixing of melts derived from a depleted mantle and a fertile mantle/plume source at the spreading center. On the other hand, type-II mafic intrusives are hornblende bearing gabbros of SSZ-type tholeiitic composition with low Ti content (TiO₂ = 0.54 wt.%–0.86 wt.%) and depleted LREE pattern with respect to HREE (La_N/Yb_N = 0.37–0.49). They also have high Ba/Zr (1.13–2.82), Ba/Nb (45.56–151.66) and Ba/Th (84.58–744.19) and U/Th ratios (0.37–0.67) relative to the primitive mantle, which strongly represents the melt composition generated by partial melting of depleted lithospheric mantle wedge contaminated by hydrous fluids derived from subducting oceanic lithosphere in a forearc setting. Their subduction related origin is also supported by presence of calcium-rich plagioclase (An_16.6–32.3). Geothermometry calculation shows that the hornblende bearing (type-II) mafic rocks crystallized at temperature in range of 565°–625 °C ± 50 (at 10 kbar). Based on these available mineralogical and geochemical evidences, we conclude that mid ocean ridge (MOR) type mafic intrusive rocks from the NMO represent the section of older oceanic crust which was generated during the divergent process of the Indian plate from the Australian plate during Cretaceous period. Conversely, the hornblende-bearing gabbros (type-II) represent the younger oceanic crust which was formed at the forearc region by partial melting of the depleted mantle wedge slightly modified by the hydrous fluids released from the subducting oceanic slab during the initial stage of subduction of Indian plate beneath the Myanmar plate.     

S,O and Pb isotopic evidence on the origin of the İnkaya (Simav-Kütahya) Cu–Pb–Zn–(Ag) Prospect,NW Turkey

The İnkaya Cu–Pb–Zn–(Ag) prospect is a typical example of the hydrothermal mineralization occurring in the Menderes Massif, which crop out in Western Anatolia. The prospect located approximately 20 km west of Simav (Kütahya-Turkey) in northern part of the Menderes Massif have been characterized through the detailed examinations involving geological, mineralogical, whole-rock geochemistry, fluid inclusion, stable isotope and lead isotope.The İnkaya Cu–Pb–Zn–(Ag) prospect is located along an E–W-trending fault in the Cambrian Simav Metamorphics, which consist of quartz–muscovite schist, quartz–biotite schist, muscovite schist, biotite schist and the Arıkayası Formation, which is composed of marbles. Galena, sphalerite, chalcopyrite, pyrite and fahlore are the main minerals, and they are accompanied by small amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, and Fe-oxides with gangue quartz. In addition to Pb, Zn, Cu, Ag, the ore samples contain substantial quantities of As, Cd and Bi and small amount of Au. Average contents of Cu, Pb, Zn and Ag are 77,400 ppm, 102,600 ppm, 6843 ppm and 203 ppm, respectively.The δ³⁴S values for galena, chalcopyrite and pyrite formed in the same stage vary in the range from − 1.7 to − 2.1‰ (average − 2.0), 0.1 to 0.3‰ (average 0.2) and − 1.5 to 2.6‰ (average + 1.5), respectively.δ³⁴S values for H₂S, representing the composition of the fluids responsible for the sulfide mineral formations and calculated from the δ³⁴S value are between − 2.77 and 1.33‰; it is consistent with the sulfur in sulfide minerals. δ¹⁸O_quartz values range from 11.3 to 16.4‰ and estimated δ¹⁸O_fluid values range from 5.4 to 10.6‰.Pyrite–galena and pyrite–chalcopyrite pairs calculated to determine equilibrium isotope temperatures based on δ³⁴S values are between 254.6 and 277.4 °C for pyrite–galena and 274.7 °C for pyrite–chalcopyrite. Sulfur and oxygen isotope values similar to the values for fluid equilibrated with an felsic magmatic source.Fluid inclusion studies on quartz of the same silicification stage coexisting with galena, sphalerite and chalcopyrite collected from the mineralized vein indicate that the temperature range of the fluids is 235 °C to 340 °C and that the salinities are 0.7 to 4.49 wt.% NaCl equivalent. The wide range of homogenization temperatures and relatively lower salinities of the fluid inclusions indicate that at least two different fluid generations were trapped in the quartz from only one fluid type. Also, lower salinities of fluid inclusion probably indicate mixing of meteoric water and magmatic fluid.The galena has ²⁰⁶Pb/²⁰⁴Pb values of 18.862–18.865, ²⁰⁷Pb/²⁰⁴Pb values of 15.707–15.711, and ²⁰⁸Pb/²⁰⁴Pb values of 39.033–39.042. The lead isotope values show a similarity with upper crustal values.     

Fluid inclusion evidence for hydrothermal fluid evolution in the Darreh-Zar porphyry copper deposit,Iran

The Darreh-Zar porphyry copper deposit is associated with a quartz monzonitic–granodioritic–porphyritic stock hosted by an Eocene volcanic sedimentary complex in which magmatic hydrothermal fluids were introduced and formed veins and alteration. Within the deepest quartz-rich and chalcopyrite-poor group A veins, LVHS2 inclusions trapped high salinity, high temperature aqueous fluids exsolved directly from a relatively shallow magma (0.5 kbar). These late fluids were enriched in NaCl and reached halite saturation as a result of the low pressure of magma crystallization and fluid exsolution. These fluids extracted Cu from the crystallizing melt and transported it to the hydrothermal system. As a result of ascent, the temperature and pressure of these fluids decreased from 600 to 415 °C, and approximately 500–315 bars. At these conditions, K-feldspar and biotite were stabilized. Type A veins were formed at a depth of ∼1.2 km under conditions of lithostatic pressure and abrupt cooling. Upon cooling and decompressing, the fluid intersected with the liquid–vapor field resulting in separation of immiscible liquid and vapor. This stage was recorded by formation of LVHS1, LVHS3 and VL inclusions. These immiscible fluids formed chalcopyrite–pyrite–quartz veins with sericitic alteration envelopes (B veins) under the lithostatic–hydrostatic pressure regime at temperatures between 415 and 355 °C at 1.3 km below the paleowater table. As the fluids ascended, copper contents decreased and these fluids were diluted by mixing with the low salinity-external fluid. Therefore, pyrite-dominated quartz veins were formed in purely hydrostatic conditions in which pressure decreased from 125 bars to 54 bars and temperature decreased from 355 to 298 °C. During the magmatic-hydrothermal evolution, the composition and P–T regime changed drastically and caused various types of veins and alterations. The abundance of chalcopyrite precipitation in group B veins suggests that boiling and cooling were important factors in copper mineralization in Darreh-Zar.     

Origin of a barite-sulfide ore deposit in the Mykonos intrusion,cyclades: Trace element,isotopic, fluid inclusion and raman spectroscopy evidence

The polymetallic Mykonos vein system in the Cyclades, Greece, consists of 15 tension-gashes filled with barite, quartz, pyrite, sphalerite, chalcopyrite and galena in ca. 13.5 Ma, I-type, Mykonos monzogranite. Zones of silica and chlorite–muscovite alteration are associated with the veins and overprint pervasive silicification, phyllic and argillic alteration that affected large parts of the monzogranite. The mineralization cements breccias and consists of an early barite–silica–pyrite–sphalerite–chalcopyrite assemblage followed by later argentiferous galena. A combination of fluid inclusion and stable isotope data suggests that the barite and associated mineralization were deposited from fluids containing 2 to 17 wt.% NaCl equivalent, at temperatures of ~ 225° to 370 °C, under a hydrostatic pressure of ≤ 100 bars. The mineralizing fluids boiled and were saturated in H₂S and SO₂.Calculated δ¹⁸O_H2O and δD_H2O, initial ⁸⁷Sr/⁸⁶Sr isotope compositions and the trace and REEs elements contents are consistent with a model in which the mineralizing fluids were derived during alteration of the Mykonos intrusion and subsequently mixed with Miocene seawater. Heterogeneities in the calculated δ³⁴S_SO4^− 2 and δ³⁴S_H2S compositions of the ore fluids indicate two distinct sources for sulfur, namely of magmatic and seawater origin, and precipitation due to reduction of the SO₄^− 2 during fluid mixing. The physicochemical conditions of the fluids were pH = 5.0 to 6.2, logf_S2 = − 13.8 to − 12.5, logf_O2 = − 31.9 to − 30.9, logf_H2S(g) = − 1.9 to − 1.7, logf_Te2 = − 7.9 and logα(SO₄^− 2_(aq)/H₂S_(aq)) = + 2.6 to + 5.5. We propose that retrograde mesothermal hydrothermal alteration of the Mykonos monzogranite released barium and silica from the alkali feldspars. Barite was precipitated due to mixing of SO₄^− 2-rich Miocene seawater with the ascending Ba-rich magmatic fluid venting upwards in the pluton.     

Compositions of biotite,amphibole, apatite and silicate melt inclusions from the Tongchang mine,Dexing porphyry deposit,SE China: Implications for the behavior of halogens in mineralized porphyry systems

The Dexing deposit, located in the Circum-Pacific ore belt, is the largest porphyry copper deposit in eastern China. It is composed of 3 separate plutons, which host three mines: Tongchang, Fujiawu and Zhushahong mines. The porphyritic granodiorite samples studied in this investigation were collected from the Tongchang ore-forming pluton of this giant deposit. This paper presents electron microprobe analyses of biotite, apatite, amphibole, plagioclase, potassium feldspar and rehomogenized glassy melt inclusions from the Tongchang porphyritic granodiorites. Petrographic observations of the samples are consistent with portions of the granodioritic magma represented by our samples being overprinted by potassic hydrothermal fluid which variably altered these minerals.All of the studied micas are Mg-rich biotites. The biotites are separated into altered magmatic and secondary types based on their petrographic and geochemical characteristics. The phlogopite components of the secondary biotites are typically higher than those of the altered magmatic biotites, and the X_Mg values of all biotites correlate negatively with Cl contents, consistent with the Mg–Cl avoidance principle. The X_Mg values also correlate negatively with (K₂O + Na₂O + BaO), FeO and TiO₂ for both generations of biotites. The calculated log (fH₂O/fHCl) values (for 690 K) of the coexisting potassic fluids, which are determined from the altered magmatic biotite compositions, range from 4.43 to 4.67, and are very similar to those of other major porphyry deposits. However, the log(fH₂O/fHF) and log(fHF/fHCl) values for the same batch of hydrothermal fluids are significant higher and lower than those of these other porphyry deposits, respectively.The Cl concentrations of amphiboles and melt inclusions range from 0.18 to 0.32 wt.% and 0.15 to 0.44 wt.%, respectively. Most apatites trapped in biotite and plagioclase phenocrysts display a bimodal Cl distribution: 0.19 to 1.35 wt.% and 1.48 to 3.73 wt.%. Similarly, the S contents of the apatite also show a distinct bimodal distribution reflecting the effects of variable anhydrite saturation during evolution of the Tongchang melt and variable dissolution of anhydrite by saline aqueous fluids. The Cl contents of the apatites from the Tongchang system are typically higher than those of other studied porphyry deposits. Furthermore, the Cl contents of the melt inclusions are at or very near the Cl saturation levels (0.36 to 0.46 wt.% at 850 °C and 50 MPa and 0.42 to 0.54 wt.% at 850 °C and 200 MPa) for these melt compositions at shallow crustal pressures. These findings suggest that the area of the granodioritic magma represented by our samples, and perhaps the bulk of the Tongchang granodioritic magma was rich in Cl. The melt inclusion compositions are consistent with a high-salinity, hydrosaline liquid being exsolved directly from the granodioritic melt directly. This high-salinity hydrosaline liquid was likely very efficient at dissolving, transporting and precipitating ore metals in the mineralizing magmatic–hydrothermal system.     

Sulfur cycling at the Mid-Atlantic Ridge: A multiple sulfur isotope approach

The role of sulfur in two hydrothermal vent systems, the Logatchev hydrothermal field at 14°45′N/44°58′W and several different vent sites along the southern Mid-Atlantic Ridge (SMAR) between 4°48′S and 9°33′S and between 12°22′W and 13°12′W, is examined by utilizing multiple sulfur isotope and sulfur concentration data. Isotope compositions for sulfide minerals and vent H₂S from different SMAR sites range from + 1.5 to + 8.9‰ in δ³⁴S and from + 0.001 to + 0.051‰ in Δ³³S. These data indicate mixing of mantle sulfur with sulfur from seawater sulfate. Combined δ³⁴S and Δ³³S systematics reveal that vent sulfide from SMAR is characterized by a sulfur contribution from seawater sulfate between 25 and 33%. This higher contribution, compared with EPR sulfide, indicates increased seawater sulfate reduction at MAR, because of a deeper seated magma chamber and longer fluid upflow path length, and points to fundamental differences with respect to subsurface structures and fluid evolution at slow and fast spreading mid-ocean ridges.Additionally, isotope data uncover non-equilibrium isotopic exchange between dissolved sulfide and sulfate in an anhydrite bearing zone below the vent systems at fluid temperatures between 335 and 400 °C. δ³⁴S values between + 0.2 to + 8.8‰ for dissolved and precipitated sulfide from Logatchev point to the same mixing process between mantle sulfur and sulfur from seawater sulfate as at SMAR. δ³⁴S values between ? 24.5 and + 6.5‰ and Δ³³S values between + 0.001 and + 0.125‰ for sulfide-bearing sediments and mafic/ultramafic host rocks from drill cores taken in the region of Logatchev indicate a clear contribution of biogenic sulfides formed via bacterial sulfate reduction. Basalts and basaltic glass from SMAR sites with Δ³³S = ? 0.008‰ reveal lower Δ³³S lower values than suggested on the basis of previously published isotopic measurements of terrestrial materials.We conclude that the combined use of both δ³⁴S and Δ³³S provides a more detailed picture of the sulfur cycling in hydrothermal systems at the Mid-Atlantic Ridge and uncovers systematic differences to hydrothermal sites at different mid-ocean ridge sites. Multiple sulfur isotope measurements allow identification of incomplete isotope exchange in addition to isotope mixing as a second important factor influencing the isotopic composition of dissolved sulfide during fluid upflow. Furthermore, based on Δ³³S we are able to clearly distinguish biogenic from hydrothermal sulfides in sediments even when δ³⁴S were identical.     

Fluid elemental and stable isotope composition of the Nibelungen hydrothermal field (8°18′S,Mid-Atlantic Ridge): Constraints on fluid–rock interaction in heterogeneous lithosphere

Depending on the geological setting, the interaction of submarine hydrothermal fluids with the host rock leads to distinct energy and mass transfers between the lithosphere and the hydrosphere. The Nibelungen hydrothermal field is located at 8°18′S, about 9 km off-axis of the Mid-Atlantic Ridge (MAR). At 3000 m water depth, 372 °C hot, acidic fluids emanate directly from the bottom, without visible sulfide chimney formation. Hydrothermal fluids obtained in 2009 are characterized by low H₂S concentrations (1.1 mM), a depletion of B (192 μM) relative to seawater, lower Si (13.7 mM) and Li (391 μM) concentrations relative to basaltic-hosted hydrothermal systems and a large positive Eu anomaly, and display a distinct stable isotope signature of hydrogen (?²H_H2O = 7.6–8.7‰) and of oxygen (?¹⁸O_H2O = 2.2–2.4‰).The heavy hydrogen isotopic signature of the Nibelungen fluids is a specific feature of ultramafic-hosted hydrothermal systems and is mainly controlled by the formation of OH-bearing alteration minerals like serpentine, brucite, and tremolite during pervasive serpentinization. New isotopic data obtained for the ultramafic-hosted Logatchev I field at 14°45′N, MAR (?²H_H2O = 3.8–4.2‰) display a similar trend, being clearly distinguished from other, mafic-hosted hydrothermal systems at the MAR.The fluid geochemistry at Nibelungen kept stable since the first sampling campaign in 2006 and is evident for a hybrid alteration of mafic and ultramafic rocks in the subseafloor. Whereas the ultramafic-fingerprint parameters Si, Li, B, Eu anomaly and ?²H_H2O distinguish the Nibelungen field from other hydrothermal systems venting in basaltic settings at similar physico-chemical conditions and are related to the interaction with mantle rocks, the relatively high concentrations of trace alkali elements, Pb, and Tl can only be attributed to the alteration of melt-derived gabbroic rocks. The elemental and isotopic composition of the fluid suggest a multi-step alteration sequence: (1) low- to medium-temperature alteration of gabbroic rocks, (2) pervasive serpentinization at moderate to high temperatures, and (3) limited high-temperature interaction with basaltic rocks during final ascent of the fluid. The integrated water/rock ratio for the Nibelungen hydrothermal system is about 0.5.The fluid compositional fingerprint at Nibelungen is similar to the ultramafic-hosted Logatchev I fluids with respect to key parameters. Some compositional differences can be ascribed to different alteration temperatures and other fluid pathways involving a variety of source rocks, higher water/rock ratios, and sulfide precipitation in the sub-seafloor at Logatchev I.