Determination of germanium isotopic compositions of sulfides by hydride generation MC-ICP-MS and its application to the Pb–Zn deposits in SW China

Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ⁷⁴Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ⁷⁴Ge. Spex and Merck standard solutions yield mean δ⁷⁴Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ⁷⁴Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ⁷⁴Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ⁷⁴Ge_pyrite < δ⁷⁴Ge_sphalerite < δ⁷⁴Gegalena, which may be controlled by the kinetic or Rayleigh fractionation.     

Copper isotopes trace the evolution of skarn ores: A case study from the Hongshan-Hongniu Cu deposit,southwest China

Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ⁶⁵Cu values (δ⁶⁵Cu = [(⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ⁶⁵Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ⁶⁵Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

Geological characteristics and genesis of the Laoshankou Fe–Cu–Au deposit in Junggar,Xinjiang, Central Asian Orogenic Belt

The Laoshankou Fe–Cu–Au deposit is located at the northern margin of Junggar Terrane, Xinjiang, China. This deposit is hosted in Middle Devonian andesitic volcanic breccias, basalts, and conglomerate-bearing basaltic volcanic breccias of the Beitashan Formation. Veined and lenticular Fe–Cu–Au orebodies are spatially and temporally related to diorite porphyries in the ore district. Wall–rock alteration is dominated by skarn (epidote, chlorite, garnet, diopside, actinolite, and tremolite), with K–feldspar, carbonate, albite, sericite, and minor quartz. On the basis of field evidence and petrographic observations, three stages of mineralization can be distinguished: (1) a prograde skarn stage; (2) a retrograde stage associated with the development of Fe mineralization; and (3) a quartz–sulfide–carbonate stage associated with Cu–Au mineralization. Electron microprobe analysis shows that garnets and pyroxenes are andradite and diopside-dominated, respectively. Fluid inclusions in garnet yield homogenization temperatures (T_h) of 205–588 °C, and salinities of 8.95–17.96 wt.% NaCl equiv. In comparison, fluid inclusions in epidote and calcite yield T_h of 212–498 and 150–380 °C, and salinities of 7.02–27.04 and 13.4–18.47 wt.% NaCl equiv., respectively. Garnets yield values of 6.4‰ to 8.9‰ δ¹⁸O_fluid, whereas calcites yield values of − 2.4‰ and 4.2‰ δ¹⁸O_fluid, and − 0.9‰ to 2.4‰ δ¹³C_PDB, indicating that the ore-forming fluids were dominantly magmatic fluids in the early stage and meteoric water in the late stage. The δ³⁴S values of sulfides range from − 2.6‰ to 5.4‰, indicating that the sulfur in the deposit was probably derived from deep-seated magmas. The diorite porphyry yields LA–MC–ICP–MS zircon U–Pb age of 379.7 ± 3.0 Ma, whereas molybdenites give Re–Os weighted mean age of 383.2 ± 4.5 Ma (MSWD = 0.06). These ages suggest that the mineralization-related diorite porphyry was emplaced during the Late Devonian, coincident with the timing of mineralization within the Laoshankou Fe–Cu–Au deposit. The geological and geochemical evidence presented here suggest that the Laoshankou Fe–Cu–Au deposit is a skarn deposit.     

Geochemical constraints on Cu–Fe and Fe skarn deposits in the Edong district,Middle–Lower Yangtze River metallogenic belt,China

Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad_29–100Gr_0–68) and diopside (Di_54–100Hd_0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)_N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (⁸⁷Sr/⁸⁶Sr)_i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)_N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (⁸⁷Sr/⁸⁶Sr)_i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ³⁴S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ³⁴S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.     

Variation of copper isotopes in chalcopyrite from Dabu porphyry Cu-Mo deposit in Tibet and implications for mineral exploration

The study presents copper (Cu) isotope data of mineral separates of chalcopyrite from four drill core samples in the Miocene Dabu porphyry Cu-Mo deposit formed in a post-collisional setting in the Gangdese porphyry copper belt, southern Tibet. Copper isotope values in hypogene chalcopyrite range from –1.48‰ to +1.12‰, displaying a large variation of up to 2.60‰, which demonstrates Cu isotope fractionation at high-temperature during hydrothermal evolution. The majority of measured chalcopyrite isotopic compositions show a gradual increasing trend from –1.48‰ to +1.12‰ with the increase of drilling depth from 130m to 483m, as the alteration assemblages change from potassic to phyllic. Similarly, the other δ⁶⁵Cu values (δ⁶⁵Cu = ((⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_standard − 1) × 1000) of the chalcopyrite show a gradual increasing trend from −1.48‰ to +0.59‰ with the decrease of drilling depth from 130 m to 57 m, as the alteration assemblages change from potassic, phyllic, through argillic to relatively fresh. These observations suggest a genetic link between Cu isotope variation and silicate alteration assemblages formed at different temperatures, indicative of a Rayleigh precipitation process resulting in the large variation of δ⁶⁵Cu values at Dabu. In general, samples closest to the center of hydrothermal system dominated by high-temperature potassic alteration are isotopically lighter, whereas samples dominated by low-temperature phyllic alteration peripheral to the center are isotopically heavier. The predicted flow pathways of hydrothermal fluids are from No. 0 to No. 3 exploration line, and the lightest δ⁶⁵Cu values are the most proximal to the hydrothermal source. Finally, we propose that the northwest side of the No. 0 exploration line has high potential for hosting undiscovered orebodies. The pattern of Cu isotope variation in conjunction with the features of silicate alteration in porphyry system can be used to trace the hydrothermal flow direction and to guide mineral exploration.     

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.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

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.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Extremely negative and inhomogeneous sulfur isotope signatures in Cretaceous Chilean manto-type Cu–(Ag) deposits,Coastal Range of central Chile

Chilean manto-type (CMT) Cu(–Ag) hydrothermal deposits share a characteristic association of volcano-sedimentary Jurassic to Lower Cretaceous host rocks, style of mineralization, ore and associated mineralogy and geochemistry, with ore grades typically > 1%Cu, that make this family of deposits significant and interesting, both academically and economically. Although often stratabound, geological evidence supports an epigenetic origin for these deposits. We present a detailed stable isotope study of La Serena and Melipilla–Naltahua Lower Cretaceous deposits, central Chile, which reveals extremely negative δ³⁴S values, to − 50‰, which are among the lowest values found in any ore deposit. In addition, the range of δ³⁴S values from sulfides in the two areas is very wide: − 38.3 to − 6.9‰ in La Serena, and − 50.4 to − 0.6‰ in Melipilla–Naltahua. These new data significantly extended the reported range of δ³⁴S data for CMT deposits. Co-existing sulfates range from 7.9 to 14.3‰, and are exclusive to La Serena deposit. The wide sulfide isotopic range occurs at deposit and hand specimen scale, and suggests a polygenic sulfur source for these deposits, where bacteriogenic sulfide dominates. While sulfur isotope data for the bulk of Jurassic CMT deposits, northern Chile, suggests a predominant magmatic source in their origin (mean = − 2.7 ± 1.9‰, 1σ), contributions of a magmatic component is only likely to be involved at Melipilla–Naltahua deposit.The δ¹³C values obtained for calcites associated with the mineralization range from − 20.1 to 0.2‰ also suggesting polygenic carbon sources, with the likely strong involvement of degradation of organic matter and leaching of limestone.Two different genetic models, with involvement of hydrocarbon, are proposed for both areas. For Melipilla–Naltahua, a two-step model can be developed as follows: 1) Framboidal pyrite growth, with very low δ³⁴S, formed by bacterial sulfate reduction in an open system, and with diagenetic degradation of oil-related brines, leaving pyrobitumen. 2) Cu-bearing stage, replacing of framboidal pyrite, inheriting depleted sulfur as low as − 50.4‰, together with sulfides directly precipitated from a hydrothermal fluid with δ³⁴S close to 0‰. For La Serena, a single step model fits best, without framboidal pyrite generation. Cu-bearing sulfides were precipitated mainly in veins where Cu plus base metal-bearing hydrothermal fluids mixed with H₂S generated by bacterial sulfate reduction in the host rocks. Isotopic evidence clearly illustrates that bacterial activity, perhaps enhanced by hydrothermal activity, was fed by hydrocarbon brines and sulfate remobilized from continental evaporites. It is possible that variable ecological conditions led to different extents of isotopic fractionation, adding to the typical sulfur isotopic heterogeneity of such bacterial systems. For both areas, the Cu-bearing stage occurred during the peak to waning stages of the very low-grade metamorphism that affected the Lower Cretaceous sequence.     

Carbon isotope stratigraphy using carbonate cements in the Triassic Sherwood Sandstone Group: Corrib Field,west of Ireland

Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ¹³C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ¹³C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ¹³C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ¹³C correlates with indicators of aridity and biological stress such that the highest δ¹³C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ¹³C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.     

Late Cretaceous magmatism and related metallogeny in the Tengchong area: Evidence from geochronological,isotopic and geochemical data from the Xiaolonghe Sn deposit,western Yunnan,China

Xiaolonghe is a poorly studied greisen-type tin deposit that is hosted by biotite granite in the western Yunnan tin belt. The mineralisation-related metaluminous and weak peraluminous granite is characterised by high Si, Al and K and low Mg, Fe and Ca, with an average A/CNK of 1.02. The granite is enriched in LILEs (K and Rb), LREEs and HFSEs (Zr, Hf, Th, U and Ce) and depleted in Ba, Nb, Sr, P, and Ti, with zircon εHf(t) = − 10.8 to − 7.5 (T_DM2 = 1.61–1.82 Ga). These characteristics indicate that the magma was generated by the partial melting of a thickened ancient crust. LA-ICP-MS U–Pb dating of igneous zircon and hydrothermal cassiterite yield ages of 71.4 ± 0.4 Ma and 71.6 ± 4.8 Ma, respectively. The igneous biotite and hydrothermal muscovite samples show Ar–Ar plateau ages of 72.3 ± 0.4 Ma and 70.6 ± 0.2 Ma, respectively. The close temporal relationship between the igneous emplacement and hydrothermal activity suggests that the tin mineralisation was closely linked to the igneous emplacement. The δ¹⁸O and δD values for the deposit range from + 3.11‰ to − 4.5‰ and from − 127.3‰ to − 94.7‰, respectively. The hydrothermal calcite C and O isotopic data show a wide range of δ¹³C_PDB values from − 5.7‰ to − 4.4‰, and the δ¹⁸O_SMOW values range from + 1.4‰ to + 11.2‰. The δ³⁴S_V-CDT data range from + 4.8‰ to + 8.9‰ for pyrite, and the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios range from 18.708 to 18.760, from 15.728 to 15.754 and from 39.237 to 39.341, respectively. The stable isotopic (C–H–O–S–Pb) compositions are all similar to those of magmatic and mantle-derived fluids, which indicate that the ore-forming fluids and materials were mainly derived from magmatic sources that were accompanied by meteoric water. The tin mineralisation in the Xiaolonghe district was closely associated with the Late Cretaceous crustal-melting S-type granites that formed during the subduction of the Neo-Tethys oceanic lithosphere. Combined with the tin deposits in the Southeast Asian tin belt, Tengchong block and Central Lhasa, we interpreted that a giant intermittent tin mineralisation belt should be present along the Asian Neo-Tethys margin.     

Geological,geochronological, and H–O isotopic constraints on the genesis of the Tongjing Cu–Au deposit in the Ningwu basin,east China

The Tongjing Cu–Au deposit is a medium-sized deposit within the Ningwu volcanic basin, east China, and is hosted by Cretaceous volcanic rocks of the Dawangshan and Niangniangshan Formations. The veined and lenticular Cu–Au orebodies are spatially and temporally related to the volcanic and subvolcanic rocks of the Niangniangshan Formation in the ore district. The wall-rock alteration is dominated by silicification, siderite alteration, carbonation, sericitization, chloritization, and kaolinization. On the basis of field evidence and petrographic observations, two stages of mineralization are recognized: (1) a siderite–quartz–sulfide stage (Stage 1) associated with the formation of chalcopyrite and pyrite in a quartz and siderite gangue; and (2) a quartz–bornite stage (Stage 2) cutting the Stage 1 phases. Stage 1 is the main mineralization stage. Quartz that formed in Stage 1 has δ¹⁸O_H2O values of − 4.3‰ to 3.5‰ with δD values of fluid inclusion waters of − 97.1‰ to − 49.9‰, indicating that the ore-forming fluids were derived from early magmatic fluids and may have experienced oxygen isotopic exchange with meteoric water during Stage 1 mineralization.LA–MC–ICP–MS zircon U–Pb dating of the mineralization-related nosean-bearing phonolite and nosean-bearing phonolitic brecciated tuff at Tongjing yields ages of 129.8 ± 0.5 Ma and 128.9 ± 1.1 Ma, respectively. These results are interpreted as the crystallization age of the volcanic rocks of the Niangniangshan Formation. A hydrothermal sericite sample associated with Cu–Au mineralization at Tongjing yields a plateau ⁴⁰Ar–³⁹Ar age of 131.3 ± 1.3 Ma. These results confirm a genetic link between the volcanism and associated Cu–Au mineralization. The Tongjing Cu–Au deposit in the Ningwu basin is genetically and possibly tectonically similar to alkaline intrusion-related gold deposits elsewhere in the world.     

Change of the ENSO-related δ18O–SST correlation from coral skeletons in northern South China Sea: A possible influence from the Kuroshio Current

Chemical proxies are useful analogs for reconstructing physical properties of sea water, such as sea surface temperature (SST) and sea surface salinity (SSS). Time series of these inferred properties would allow for reconstructions of past El Niño–Southern Oscillation (ENSO) events, where no instrumental records exist. In this study, a monthly oxygen isotope record from a Porites coral is used to explain how past ENSO events are recorded in the coral skeletons. The sample covers a 12 year period and was collected from Nanwan Bay, Taiwan. During El Niño events the coral skeleton is shown to produce a δ¹⁸O–SST correlation with a slope of −0.12 ± 0.04‰ °C⁻¹. During other times, this value is significantly different, with a slope of −0.21 ± 0.04‰ °C⁻¹. Coral that grew during El Niño summers have δ¹⁸O values which are enriched by ∼0.2‰, relative to other times. A possible mechanism to explain this difference may be enhanced penetration of Kuroshio Current waters into the South China Sea during summer. The observed contrast in the correlation of δ¹⁸O–SST variability in this sample supports the influence of El Niño in eastern Asia.     

A magmatic source of hydrothermal sulfur for the Prominent Hill deposit and associated prospects in the Olympic iron oxide copper-gold (IOCG) province of South Australia

The Prominent Hill deposit is a world-class iron oxide copper–gold (IOCG) deposit in South Australia, characterized by a high Cu/S ratio of the dominant Cu-(Fe) sulfides hosted by hematite breccias. It contains a total resource of 278 Mt of ore at 0.98% Cu and 0.75 g/t Au. Prominent Hill is one of several IOCG deposits and numerous prospects in the Olympic IOCG province that are temporally associated with the 1603–1575 Ma Gawler Range Volcanics, a large igneous province including co-magmatic granitoid intrusions of the Hiltaba Suite. Globally, IOCG deposits share many similar features in terms of their geological environment and mineral association. However, it is not yet clear whether sulfur and copper originate from the same source rocks and which hydrothermal redox processes created the characteristic iron oxide enrichment. Highly variable sulfur isotope compositions of sulfides and sulfates in IOCG deposits have previously been interpreted in terms of diverse sulfur sources that may include contributions from magmatic, sedimentary, seawater or evaporitic sulfur. In order to test these alternatives, we performed a detailed sulfur isotope study of Cu-(Fe) sulfides from Prominent Hill and IOCG prospects nearby. The Prominent Hill deposit shows a wide range in δ³⁴S_V-CDT between − 33.5‰ and 29.9‰ for Cu-(Fe) sulfides, and a narrower range of 4.3‰ to 15.8‰ for barite. Iron sulfides (pyrite, pyrrhotite) show a narrow range in sulfur isotope composition, whereas Cu-bearing sulfides show a much wider range, and more negative δ³⁴S_V-CDT values on average. We propose a two-stage sulfide mineralization model for the IOCG system in the Prominent Hill area, in which all hydrothermal sulfur is ultimately derived from a magmatic source that had a composition of 4.4 ± 2‰. The diversity in sulfur isotope composition can be produced by different fluid evolution pathways along reducing or oxidizing trajectories. A reduced sulfur evolution pathway is responsible for stage I mineralization, when intrusion-derived magmatic-hydrothermal fluids produced early pyrite and minor chalcopyrite at Prominent Hill, and iron ± copper sulfides in regional magnetite skarns and in some pervasively altered volcanic rocks of the Gawler Range Volcanics. Shallow-venting magmatic-hydrothermal fluids and subaerial volcanic gases that became completely oxidized by reaction with atmospheric oxygen produced sulfate and sulfuric acid with a sulfur isotope composition equal to their magmatic source. This highly oxidized ore fluid probably consisted dominantly of water from the hydrosphere, but contained magmatic solute components, notably sulfate, acidity and Cu. Sulfate reduction produced hydrothermal Cu sulfides with a wide range in sulfur isotope compositions from very negative to moderately positive values. Partial reaction of the Cu-rich stage II fluid with earlier stage I sulfides resulted in mixing of sulfur derived from sulfate reduction and from sulfides deposited during stage I. Modeling of the sulfur isotope fractionation processes in response to reducing and oxidizing pathways demonstrates that the entire spectrum of sulfur isotope data from stage I and stage II mineralization can be explained with a single, ultimately magmatic sulfur source. Such a magmatic sulfur source is also adequate to explain the complete spectrum of sulfur isotope data of other IOCG prospects and deposits in the Olympic province, including Olympic Dam. The results of our study challenge the conventional model that suggests the requirement of multiple and compositionally diverse sulfur sources in hematite-breccia hosted IOCG style mineralization.     

Some new data on the genesis of the Linghou Cu–Pb–Zn polymetallic deposit—Based on the study of fluid inclusions and C–H–O–S–Pb isotopes

The Linghou deposit, located near Hangzhou City of Zhejiang Province, eastern China, is a medium-sized polymetallic sulfide deposit associated with granitic intrusion. This deposit is structurally and lithologically controlled and commonly characterized by ore veins or irregular ore lenses. In this deposit, two mineralization events were identified, of which the former produced the Cu–Au–Ag orebodies, while the latter formed Pb–Zn–Cu orebodies. Silicification and calc-silicate (skarn type), phyllic, and carbonate alternation are four principal types of hydrothermal alteration. The early Cu–Au–Ag and late Pb–Zn–Cu mineralizations are characterized by quartz ± sericite + pyrite + chalcopyrite + bornite ± Au–Ag minerals ± magnetite ± molybdenite and calcite + dolomite + sphalerite + pyrite + chalcopyrite + galena, respectively. Calcite clusters and calcite ± quartz vein are formed during the late hydrothermal stage.The NaCl–H₂O–CO₂ system fluid, coexisting with NaCl–H₂O system fluid and showing the similar homogenization temperatures (385 °C and 356 °C, respectively) and different salinities (16.89–21.68 wt.% NaCl eqv. and 7.70–15.53 wt.% NaCl eqv.), suggests that fluid immiscibility occurred during the Cu–Au–Ag mineralization stage and might have given rise to the ore-metal precipitation. The ore-forming fluid of the Pb–Zn–Cu mineralization mainly belongs to the NaCl–H₂O–CO₂ system of high temperature (~ 401 °C) and mid-high salinity (10.79 wt.% NaCl eqv.).Fluids trapped in the quartz-chalcopyrite vein, Cu–Au–Ag ores, Pb–Zn–Cu ores and calcite clusters yielded δ¹⁸O_H2O and δD values varying from 5.54‰ to 13.11‰ and from − 71.8‰ to − 105.1‰, respectively, indicating that magmatic fluids may have played an important role in two mineralization events. The δ¹³C_PDB values of the calcite change from − 2.78‰ to − 4.63‰, indicating that the CO₃^2 − or CO₂ in the ore-forming fluid of the Pb–Zn–Cu mineralization was mainly sourced from the magmatic system, although dissolution of minor marine carbonate may have also occurred during the ore-forming processes. The sulfide minerals have homogeneous lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb ranging from 17.958 to 18.587, ²⁰⁷Pb/²⁰⁴Pb ranging from 15.549 to 15.701, and ²⁰⁸Pb/²⁰⁴Pb ranging from 37.976 to 39.052, indicating that metallic elements of the Linghou deposit came from a mixed source involving mantle and crustal components.Based on geological evidence, fluid inclusions, and H–O–C–S–Pb isotopic data, the Linghou polymetallic deposit is interpreted as a high-temperature, skarn-carbonate replacement type. Two types of mineralization are both related to the magmatic–hydrothermal system, with the Cu–Au–Ag mineralization having a close relationship with granodiorite.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Alteration mineralogy,lithochemistry and stable isotope geochemistry of the Murgul (Artvin,NE Turkey) volcanic hosted massive sulfide deposit: Implications for the alteration age and ore forming fluids

The Murgul (Artvin, NE Turkey) massive sulfide deposit is hosted dominantly by Late Cretaceous calc-alkaline to transitional felsic volcanics. The footwall rocks are represented by dacitic flows and pyroclastics, whereas the hanging wall rocks consist of epiclastic rocks, chemical exhalative rocks, gypsum-bearing vitric tuff, purple vitric tuff and dacitic flows. Multi-element variation diagrams of the hanging wall and footwall rocks exhibit similar patterns with considerable enrichment in K, Rb and Ba and depletion in Nb, Sr, Ti and P. The chondrite-normalized rare earth element (REEs) patterns of all the rocks are characterized by pronounced positive/negative Eu anomalies as a result of different degrees of hydrothermal alteration and the semi-protected effects of plagioclase fractionation.Mineralogical results suggest illite, illite/smectite + chlorite ± kaolinite and chlorite in the footwall rocks and illite ± smectite ± kaolinite and chlorite ± illite in the hanging wall rocks. Overall, the alteration pattern is represented by silica, sericite, chlorite and chlorite–carbonate–epidote–sericite and quartz/albite zones. Increments of Ishikawa alteration indexes, resulting from gains in K₂O and losses in Na₂O and the chlorite–carbonate–pyrite index towards to the center of the stringer zone, indicate the inner parts of the alteration zones. Calculations of the changes in the chemical mass imply a general volume increase in the footwall rocks. Abnormal volume increases are explained by silica and iron enrichments and a total depletion of alkalis in silica zone. Relative K increments are linked to the sericitization of plagioclase and glass shards and the formation of illite/smectite in the sericite zone. In addition, Fe enrichment is always met by pyrite formation accompanied by quartz and chlorite. Illite is favored over chlorite, smectite and kaolinite in the central part of the ore body due to the increase in the (Al + K)/(Na + Ca) ratio. Although the REEs were enriched in the silicification zone, light REEs show depletion in the silicification zone and enrichment in the other zones in contrast to the heavy REEs' behavior. Hydrothermal alteration within the hanging wall rocks, apart from the gypsum-bearing vitric tuffs, is primarily controlled by chloritization with proportional Fe and Mg enrichments and sericitization.The δ¹⁸O and δD values of clay minerals systematically change with increasing formation temperature from 6.6 to 8.7‰ and − 42 to − 50‰ for illites, and 8.6 and − 52‰ for chlorite, respectively. The O- and H-stable isotopic data imply that hydrothermal-alteration processes occurred at 253–332 °C for illites and 136 °C for chlorite with a temperature decrease outward from the center of the deposit. The positive δ³⁴S values (20.3 to 20.4‰) for gypsum suggest contributions from seawater sulfate reduced by Fe-oxide/-hydroxide phases within altered volcanic units. Thus, the hydrothermal alteration possibly formed via a dissolution–precipitation mechanism that operated under acidic conditions. The K–Ar dating (73–62 Ma) of the illites indicates an illitization process from the Maastrichtian to Early Danian period.