Possible Carbonate Origin of Ore Sulfur from Geumseong Mo Deposit, South Korea

Abstract: In order to know the cause of the high δ³⁴S values of the Korean ore deposits (Ishihara et al., 2000), Geumseong molybdenum skarn deposit and related Jurassic granitoids and Cambro-Ordovician carbonates were selected for the δ³⁴S analyses. Two sulfide samples occurring in hydrothermal veins in fresh granitoids quarry at Songhaksan yielded δ³⁴S values of +6.9 and +8.8 permil. These are slightly higher than +5.3 permil δ³⁴S of the averaged rock sulfides for the Jurassic Daebo granitoids. Pyrite and molybdenite from the Geumseong deposit vary from +8.6 to +11.5 permil (average + 10.7 permil). The intruded carbonates contain very low amount of SSS (structurally substituted sulfate) as 2.9 to 8.1 ppm with high δ³⁴S values between +28.8 and + 40.0 permil, and sulfides sulfur of 52 to 779 ppm with variable δ³⁴S values between +3.2 and +22.5 per–mil. It is concluded that sulfur of the host carbonates was extracted and migrated into the skarn deposit at the time of the granitoid intrusion and the related hydrothermal convection, on the basis of the location of the skarn deposit occurring between the carbonates and Jurassic granitoids, and of very low contents of SSS sulfur in the carbonates. A part of SSS possibly contaminated into the Jurassic granite.     

Sulfur Isotope Study of Precambrian Basement and Mesozoic Intrusive Rocks in the Southwestern Part of Ryeongnam Massif, Korea

Abstract. Isotope composition of whole rock sulfur has been measured on 14 schists, 10 gneisses, 7 gabbroids, 7 granitoids and 2 sedimentary rocks, with of 9 sulfide (pyrite) sulfurs in gabbros and granitoids, from the southwestern part of the Ryeongnam Massif, Korea. The δ³⁴S values of schists range from -4.6 to +6.1 % (average +0.9 %), those of gneisses from -4.0 to +0.8 % (-1.9%), those of gabbroids from -2.3 to +3.7 % (+1.0 %), and those of granitoids from -5.9 to +3.2 % (-1.9 %). The δ³⁴S values of pyrite separated from gabbros and granitoids show rather heavier values ranging from +3.1 to +9.4 % with an average of+5.8%.
Though the δ³⁴S values of whole rock sulfur give wide range of -5.9 to +6.1 %, the average of about -0.5 % is close to the mantle value. The granitoids sampled at the central parts of intrusive bodies or at the contacts with other plutonic rocks tend to show positive values, while those sampled near the boundary with basement rocks such as granitic gneiss and por-phyroblastic gneiss show negative values. Though the reason of this tendency is not clear at present, the δ³⁴S values of some granitoids in this area seem to represent possible influence by the assimilation of country rocks, particularly of gneisses.
Average isotopic compositions of ore sulfur from individual metal deposits in the studied area are summarized to have a range of+1.0 to +7.8 % with an average value of+3.2 %. The values are consistent with the previous finding that the ore sulfur isotopic values of the Ryeongnam Massif are the lowest among the four tectonic belts in Korea; Gyeonggi Massif, Ogcheon Belt, Ryeongnam Massif, and Gyeongsang Basin. This feature may reflect the isotopic compositions of plutonic rocks and basements in this area, which are characterized by relatively low values around zero permil.     

Sulfur Isotope Geochemistry of the Supergiant Xikuangshan Sb Deposit, Central Hunan, China: Constraints on Sources of Ore Constituents

Abstract. The supergiant Xikuangshan Sb deposit is located in the Middle to Upper Devonian limestone of central Hunan, China. Primary ores are composed of early-stage stibnite and calcite with rare pyrite, early main-stage stibnite and quartz, and late main-stage stibnite and calcite. New sulfur isotope data reveal the clustering of δ³⁴S values (+5 ∼ +8 %) for both early and late main-stage stibnite; a single early-stage stibnite exhibits δ³⁴S value (+7.5 %) identical to its main ore-stage counterparts and the coexisting calcite has almost unmodified carbon isotope composition (-4.4 %). The data suggest a probable common source of sulfur for stibnite that was deposited at different paragenetic stages. A much wider variation in δ³⁴S values for early main-stage stibnite (+3.5 to +16.3 %, av. +7.5 %) compared to that for late main-stage stibnite (+5.3 to +8.1 %, av. +6.2 %) can be interpreted to be due to local interaction of earlier ore fluid with Devonian host rocks. The previous studies show that the Precambrian basement contains elevated Sb concentrations, and two distinctive sulfur reservoirs with δ³⁴S_pyrite values at ca. +11 ∼ +24 % and -7.0 ∼-11 %. The homogenizing effect for sulfur hydrothermally leached from the two reservoirs might have provided ore constituents for the Xikuangshan fluids.     

Hydrogen, Oxygen and Sulfur Isotope Studies of Seafloor Hydrothermal System at the Desmos Caldera, Manus Back-arc Basin, Papua New Guinea: An Analogue of Terrestrial Acid Hot Crater-lake

Abstract. The Onsen site is an active submarine hydrothermal system hosted by the Desmos caldera in the Eastern Manus Basin, Papua New Guinea. The hydrothermal fluid is very acidic (pH=1.5) and abundant native sulfur is deposited around the vent. The δ³⁴S values of native sulfur range from -6.5 to -9.3 %o. δ³⁴S values of H₂S and SO₄ in the hydrothermal fluid are -4.3 to -9.9 %o and +18.6 to +20.0 %o, respectively. These δ³⁴S values are significantly lower than those of the other hydrothermal systems so far reported. These low δ³⁴S values and the acidic nature of the vent fluids suggest that volcanic SO₂ gas plays an important role on the sulfur isotope systematic of the Onsen hydrothermal system. Relationship among the δ³⁴S values of S-bearing species can be successively explained by the model based on the disproportionation reaction starting from the volcanic SO₂ gas. The predicted δ³⁴S values of SO₂ agree with the measured whole rock δ³⁴S values. δD and δ¹⁸O values of clay minerals separated from the altered rock samples also suggest the contribution of the magmatic fluid to the hydrothermal system. Present stable isotopic study strongly suggests that the Onsen hydrothermal site in the Desmos caldera is a magmatic submarine hydrothermal system.     

Sulfur Isotopic Study of the Toyoha Deposit, Hokkaido, Japan Comparison between the Earlier-Stage and the Later-Stage Veins

Abstract: The sulfur isotopic ratios (δ³⁴S) of ore minerals from the Toyoha deposit, Hokkaido, one of the largest Pb–Zn–Ag polymetallic vein-type deposits in Japan, were studied. More than 90% of the δ³⁴S values of the studied sulfide minerals collected from the Toyoha deposit range from +5 to +9%, with an average of approximately +7% irrespective of the mineral species, veins, elevations, depth, mineralization stages and mineral assemblages. Relatively uniform δ³⁴S values obtained in this study suggest that the reduced aqueous sulfur species predominated over the oxidized sulfur in the ore solution throughout the mineralization stages. Thus, the source of sulfur for the ore sulfides is postulated to be magmatic.
The temperature obtained from the fluid inclusion study and the temperature of the sulfur isotopic geothermometer are not consistent. This suggests that each mineral precipitated under disequilibrated conditions with respect to the sulfur isotope.
The change in redox conditions presumably encountered between the mineralization stages did not account for the isotopic fluctuations since the isotopic exchanges between the oxidized and reduced aqueous sulfurs are much slower than the rate of oxidation of the ore solution.     

Trace Fossils and Sulfur Isotopes in Mudstones around the Kuroko Deposits in the Hokuroku Basin, Northeast Japan: An Attempt to Delineate the Depositional Environment

Abstract. A comprehensive investigation was carried out on the distribution of both trace fossils and sulfur isotopes in mud-stones in the Hokuroku district, northeast Japan, in the hope of delineating the depositional environment of the mudstones in which the Kuroko deposits are embedded. The mudstones are generally massive in structure and usually contain large trace fossils, being indicative of an aerobic biofacies. On the other hand, some mudstones in and above the Kuroko ore horizon are partly laminated and usually contain smaller trace fossils, being assignable to an anaerobic or dysaerobic biofacies. The δ³⁴S values of sulfides in the mudstones above and below the ore horizon range from -40 to -12 %o, indicating mostly oxic depositional conditions in equilibrium with the inferred aerobic biofacies. In the mudstones in the ore horizon, the δ³⁴S values exhibit regionally discriminated variations: -44 to -12 %o in areas far (>1 km) from the known Kuroko deposits and -24 to +6 %o in areas closer to them. The latter high δ³⁴S group implies the temporal occurrence of local anoxic basins in the vicinity of the known Kuroko deposits. At the time of late Nishikurosawa Stage (i.e. the currently assumed Kuroko metallogenic epoch), an intense oceanic stagnation is suggested to have taken place to form the local anoxic basins responsible for the formation and preservation of Kuroko deposits. This oceanic environmental event is considered to be most likely due to increasing biological productivity primarily triggered and enhanced by upwelling of NADW in the paleo-Sea of Japan at that time.     

Heavy Sulfur-isotope Enrichment in Middle Miocene Onnagawa Mudstones in the Green Tuff Region, Northeastern Japan

Abstract. Sulfur isotope ratios are analyzed for a series of mudstones in a successive section in the Taiheizan area in the central Green Tuff region, northeast Japan. The δ³⁴S values for the Uyashinai Mudstone Member (Nishikurosawa stage), the Onnagawa Formation and the Funakawa Formation range from -45 to -14%, -20 to +4% and -30 to -10%, respectively. There is a marked positive shift in δ³⁴S values at the Nishikurosawa/Onnagawa boundary and an upward δ³⁴S-decreasing trend in the Onnagawa and Funakawa Formations. The present data provides evidence for environmental change in the form of stratification of the seawater, initiated at the Nishikurosawa/Onnagawa boundary and persisting during deposition of the Onnagawa Formation, followed by gradual oxygenation during deposition of the Funakawa Formation.     

A widespread positive δ13Ccarb anomaly at around 2.33–2.06 Ga on the Fennoscandian Shield: a paradox?

Carbon isotope measurements carried out on 201 carbonate samples from the early Proterozoic of the Kola Peninsula, N. Karelia and Norway yield δ¹³C (PDB) spanning - 20.5% to + 11%. A general δ¹³C secular trend shows that prior to 2.33 Ga values are typically 'normal' marine, averaging around - 3%0. Between 2.33 and 2.06 Ga, in Jatulian time, there follows a rapid excursion to positive δ¹³C of around + 6%. Post-Jatulian time is characterized by δ¹³C of sedimentary carbonates fluctuating between - 5% and +3%; also it is remarkable for the first pronounced development of diagenetic carbonates, which have δ¹³C between - 14 % and - 6% . The c. 6% positive δ¹³C shift with a duration of about 270 Myr coincides with a maximum in the diversity and abundance of stromatolites, and with widespread development of 'red beds', but does not coincide with the maximum of buried C_org mass. The Fennoscandian Shield represents the largest isotoically anomalous carbonate province yet reported, and the positive δ¹³C excursion together with a series of major global palaeoenviromental changes seems to be more intense than the Precambrian/Cambrian transition events. However, it is still not clear what kind of mechanism this phenomenon could be attributed to. An increase of the 'Ronov ratio', and/or 'Broecker ratio' and other possible models are discussed as the target for future investigations.     

Origin of Bornite Pods in Intrusive Rocks at the Kingking Porphyry Copper-gold Deposit, Southeastern Mindanao, Philippines

At the Kingking porphyry copper-gold deposit, Compostela Valley, south-eastern Mindanao, Philippines, bornite pods occur in the brecciated parts in the biotite diorite porphyry, together with the volcanic rock and diorite fragments without associated stockworks of quartz veinlets. These pods are generally elongated in shape and measure several centimeters across their longest axes. They are composed of bornite and chalcopyrite with traces of calaverite. The δ³⁴S of bornite and subordinate chalcopyrite of bornite pods ranging from −2.2‰ to +0.1‰ are similar to the δ³⁴S of sulfides associated with quartz veinlets such as bornite and chalcopyrite ranging from −4.7‰ to ±0.0‰. This suggests that the ultimate source of sulfur is identical for bornite pods and sulfides associated with quartz veinlets. Bornite pods are associated with volcanic rock and dioritic fragments in the brecciated portion of the biotite diorite porphyry. It was observed that some dioritic fragments contain quartz veinlets, which may indicate an earlier episode of mineralization. Fragments of the earlier dioritic intrusive rocks and the volcanic rocks, together with the sulfides were incorporated into the biotite diorite porphyry magma. A molten sulfide is possible for the composition between bornite and intermediate solid solution at ∼800°C. The sulfides from the earlier dioritic intrusive rocks in the molten state were segregated and then eventually coalesce to form the bornite pods in the brecciated section of the biotite diorite porphyry.     

A new source of isotopically heavy sulphur in lode-gold deposits of NW Spain: a batch volatilization process in the conversion of pyrite to pyrrhotite by contact metamorphism

The conversion of pyrite to pyrrhotite is identified in this study as a new source of isotopically heavy sulphur in thermal domes. Contact metamorphism of a sequence of pyrite-rich shales by the Penedela blind intrusion (NW Spain) causes the conversion of diagenetic pyrite to pyrrhotite at a temperature of 150 °C. This process occurred in a closed system with total consumption of the diagenetic pyrite and production of H₂S-rich fluids. The H₂S liberated in this unidirectional reaction shows a relatively heavy δ³⁴S, in agreement with a batch volatilization process. The mixture of this H₂S-rich fluids with derived sulphur from Lower Cambrian carbonates produced gold-bearing pyrite at a temperature of 340 °C. The contribution from these two different sulphur sources was 86% and 14%, respectively. The metamorphic fluids migrated through permeable zones such as fractures and shear zones, producing a lode-gold deposit.     

40Ar-39Ar Spectra of Alunite from Phreatic Craters in the Muine Volcano, Hokkaido, Japan

Abstract. ⁴⁰Ar-³⁹Ar analyses of two alunite samples from phreatic craters in the Pliocene Muine volcano in southwest Hokkaido, Japan, were carried out. The alunite with 17.4 permil δ³⁴S_{V_CDT} value in hydrothermal breccia from the Nagaoyama crater and that with 14.3 permil δ³⁴S_{V_CDT} value in silicified andesite from the Konuma crater give total fusion ages of 1.40 ± 0.04 Ma (la uncertainty) and 1.24 ± 0.08 Ma, respectively. However, the spectra of these samples indicate they have been effected by thermal overprinting and/or the existence of excess argon. These preliminary ⁴⁰Ar-³⁹A analyses suggest that the alunite underwent multiple hydrothermal activity by magmatic gas and vapor subsequent to the main hydrothermal activity.     

Oxygen Isotopic Characteristics of Granitic Intrusions Related to Haobugao Zn-Pb-Cu-Sn Skarn Deposit, East Inner Mongolia, China

Abstract. Granitic rocks related to the formation of Haobugao Zn-Pb-Cu-Sn skarn deposit, Inner Mongolia, China, show unusual low whole-rock δ¹⁸O values down to -8.8 % (V-SMOW), whereas separated quartz crystals from those rocks give positive δ¹⁸O values of+4.1 to +9.9 %. Chemical analyses and microscopic observation of those granitic rocks confirm that they suffered hydrothermal alteration. Some skarn specimens and quartz from the Haobugao deposit also show negative δ¹⁸O values. The isotopic evidence indicates that intensive meteoric water circulation occurred at the time of granitic intrusion, and caused the pervasive hydrothermal alteration of granitic rocks and the precipitation of skarn deposit in this area.     

Stable Isotope Study of the Langshan Polymetallic Mineral District, Inner Mongolia, China

Abstract: A comprehensive stable isotope investigation was carried out to clarify the geneses of the ore deposits in the Langshan Pb-Zn mineral district. The lead isotope study shows that these deposits were probably formed from 2. 0 to 1. 5 Ga, and were deformed and metamorphosed 1. 45 Ga. Ore lead could be a mixture of mantle lead and crustal lead. The C and S isotope results indicate that these deposits were precipitated in closed or semi-closed rift basins, and the source of sulfur might be Proterozoic ocean sulfate. The H and O isotope results indicate that the δD and δ¹⁸O values of rocks were changed by water-rock interaction during metamorphism and hydrothermal alteration. The scale of δD and δ¹⁸O shift of rocks reflects the grade of metamorphism and alteration as well as the water-rock ratios. However, the water-rock ratios in the metamorphic processes of Langshan mineral district were relatively low, and the source of water during metamorphism is suggested to be ancient meteoric water. Based on isotopic results and the geological background, it is concluded that these deposits may belong to Proterozoic sedimentary exhalative (SEDEX) type.     

Sulfur isotope ratios of Icelandic rocks

Sulfur isotope ratios have been determined in 27 selected volcanic rocks from Iceland together with their whole rock chemistry. The ³⁴S of analyzed basalts ranges from –2.0 to +0.4 with an average value of –0.8 Tholeiitic and alkaline rocks exhibit little difference in ³⁴S values but the intermediate and acid rocks analyzed have higher ³⁴S values up to +4.2 It is suggested that the overall variation in sulfur isotope composition of the basalts is caused by degassing. The small range of the ³⁴S values and its similarity to other oceanic and continental basalts, suggest that the depleted mantle is homogeneous in its sulfur isotope composition. The ³⁴S of the depleted mantle is estimated to be within the range for undegassed oceanic basalts, –0.5 to +1.0     

Foraminiferal changes and geochemical profiles across the Cenomanian/Turonian boundary in central and south-east Poland

Two sections of the Upper Cenomanian and Lower Turonian in central and south-east Poland were investigated for foraminifers, CaCO₃content, carbon content insoluble in HCl (C_org) and in the carbonates (C_carb), carbon and oxygen isotopic composition of bulk-rock carbonates and elemental abundances. The Cenomanian/Turonian boundary interval is characterized by the appearance of more marly facies, a δ¹³C and δ¹⁸O stable isotope anomaly, a considerable increase in C_org content and decrease in C_carb content and substantial changes in the foraminiferal assemblages. A major carbon stable isotope excursion with a shift of +2 (PDB) occurs in the lowermost Whiteinella archaeocretacea Zone. The late Cenomanian δ¹³C anomaly is associated with heavy δ¹⁸O values. The peak value of δ¹³C corresponds to the minima in P/B ratio and in diversity of foraminiferal assemblages. A late Cenomanian anoxic event is thought to be responsible for changes in foraminiferal assemblages. However, elemental abundance analyses do not show changes in the concentrations of trace elements. This may be explained by the long distance between studied area and a source of enrichment which was probably located in the western hemisphere.     

Sulfur isotope studies of the felbertal scheelite deposit,eastern alps

The Felbertal scheelite deposit is the largest known strata-bound tungsten concentration. It lies in an up to 400 m thick rock pile in the lowermost part of the volcanic rock sequence, probably of the Early Paleozoic Habach Formation. Both ore fields (eastern and western) have been affected by Variscan and Alpine metamorphism and tectonism, resulting in a remobilization of the ore mineralization. This ore deposit and the neighboring rocks show a strikingly low sulfur content. The eastern field with one major orebody has very little sulfide mineralization. The western field, with 8 orebodies (K1–K8) and two remobilized vein zones (S1 and S2), reveals somewhat more minor sulfide enrichments that are mainly within and around the K1 and K2 orebodies and in some parts of the interlayered schist sequence. Sulfur isotope compositions of 90 sulfide minerals (37 pyrrhotite, 20 chalcopyrite, 19 pyrite and 11 molybdenite and/or WS₂-MoS₂ solid solutions and 3 Pb-Bi sulfosalts, including 7 sulfides within scheelite grains) from 60 ore and host rock samples have been determined with a standard error of less than ±0.2 per mil. All data range from –3.6 to +4.3 ³⁴S. There are small differences in the sulfur isotope values from place to place and in time from the first and second to the third generation. In the western field, the K1 orebody differs from other orebodies (K2, K4, K7) due to isotopically heavier ³⁴S values. The three scheelite generations show differences in the ³⁴S values of the sulfide microphases within scheelite grains, from +1.0 to +4.3 per mil for the first and the second, and from –1.8 to –3.3 per mil for the third generation. Sulfide phases within molybdoscheelites may have crystallized under the same conditions as the other coeval sulfide minerals in the same orebody. They commonly formed later than scheelite. These changes may be explained using data from Ohmoto and Rye (1979): Small changes in temperature, pH, and/or may result in large changes in the ³⁴S values with the precipitation of isotopically heavier sulfides under more reducing conditions. Only four samples with sulfide mineral pairs show isotopic equilibrium. All others display some disequilibrium. We suggest that the sulfides in the ores and surrounding volcanogenic host rocks formed contemporaneously from the same hydrothermal ore fluids, and that the sulfur species in these fluids may have been dominantly H₂S.     

Polymetallic Mineralization at the Nakakoshi Copper Deposits, Central Hokkaido, Japan

Abstract: Polymetallic mineralization at the Nakakoshi deposits, Kamikawa town, central Hokkaido, occur as fracture-filling veins in Cretaceous slate of the Hidaka Supergroup. Ten veins have been recognized in NE-SW and E-W directions. Sericite in altered slate which is the host of the deposits, was dated at 31. 1 Ma, Oligocene in age.
No. 9 vein consists of massive chalcopyrite ore with various kinds of minerals such as pyrite, pyrrhotite, arsenopyrite, sphalerite, tetrahedrite, Ag-minerals and Cu–Zn–Fe–In–Sn–S minerals, quartz and sericite. Chalcopyrite and pyrite contain sphalerite star and sphalerite with chalcopyrite emulsions. Maximum indium contents of sphalerite and the Cu–Zn–Fe–In–Sn–S minerals are 1. 8 and 16. 3 wt%, respectively. The sulfur isotopic ratios, δ³⁴S of ore minerals, range from –12. 9 to –9. 6%. Formation temperatures of the sulfide minerals are estimated as 300–500°C, based on the paragenesis and chemical compositions of the minerals.     

Sulfur, lead and helium isotopic compositions of sulfide minerals from the Dachang Sn-polymetallic ore district in South China: implication for ore genesis

Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ³⁴S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ³⁴S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ³⁴S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb or ²⁰⁸Pb/²⁰⁴Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The ³He/⁴He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material     

Sulfur isotope evidence for penetration of MVT fluids into igneous basement rocks,southeast Missouri,USA

Previous studies of galena and sphalerite from Paleozoic MVT deposits in the Viburnum Trend, southeast Missouri documented large variations in ³⁴S values throughout the ore-forming event. The present study of Cu-Fe-sulfides reveals a similar ³⁴S variation that reflects two end-member sulfur reservoirs whose relative importance varied both temporally and spatially. More ³⁴S-enriched sulfides (³⁴S approaching 25) indicate introduction of sulfur from basinal sedimentary sources, whereas more ³²S-enriched sulfides (³⁴S < 5) may reflect fluids moving through underlying granitic basement. Two areas containing Precambrian, igneous-hosted FeCu mineralization in southeast Missouri (West and Central Domes of Boss-Bixby) were investigated to elucidate their relationship to Cu-rich MVT orebodies hosted nearby within the overlying Cambrian Bonneterre Dolomite. Mineralization at Boss-Bixby is composed of an early phase of iron oxide deposition followed by Cu-Fe-sulfides. The Central Dome is faulted and its mineralization is more fracture-controlled than the typically podiform ores of the West Dome. The ³⁴S values of West Dome sulfides are 0.9 to 6.5 and pyrite-chalcopyrite indicate a temperature of 525° ± 50 °C. These data indicate an igneous source of sulfur during Precambrian ore deposition. In contrast, ³⁴S values of Central Dome sulfides are 9.4 to 20.0 and pyrite-chalcopyrite indicate temperatures of 275° ± 50 °C. Similar ³⁴S values are obtained for chalcopyrite from the overlying MVT deposits. We speculate that deeply circulating, basin-derived MVT fluids mobilized sulfur and copper from the underlying igneous basement and redeposited them in overlying Curich MVT orebodies, as well as overprinting earlier Precambrian sulfides of the Central Dome with a later, Paleozoic MVT sulfur isotope signature. Many models for MVT fluid circulation in the Midcontinent region of North America assume that igneous basement rocks are an impermeable boundary, but in southeast Missouri, evidence exists for structurally controlled MVT fluid movement > 600 m vertically through underlying Precambrian igneous rocks. Such basement involvement has been suggested for other carbonate-hosted base-metal districts (e.g. Irish base metal deposits) and should be considered an integral part of the ore-forming process in southeast Missouri.     

Distinguishing Cambrian from Upper Ordovician source rocks: Evidence from sulfur isotopes and biomarkers in the Tarim Basin

The reported source rocks for the abundant petroleum in the Tarim Basin, China range from Cambrian to Lower Ordovician and/or Upper Ordovician in age. However, the difference between the two groups of source rocks is not well characterized. In this study, pyrite was removed from eleven mature to over mature kerogen samples from source rocks using the method of CrCl₂ reduction and grinding. The kerogen and coexisting pyrite samples were then analyzed for δ³⁴S values. Results show that the kerogen samples from the Cambrian have δ³⁴S values between +10.4‰ and +19.4‰. The values are significantly higher than those from the Lower Ordovician kerogen (δ³⁴S of between +6.7‰ and +8.7‰), which in turn are generally higher than from the Upper Ordovician kerogen samples (δ³⁴S of between ?15.3 and +6.8‰). The associated pyrite shows a similar trend but with much lower δ³⁴S values. This stratigraphically controlled sulfur isotope variation parallels the evolving contemporary marine sulfate and dated oil δ³⁴S values from other basins, suggesting that seawater sulfate and source rock age have an important influence on kerogen and pyrite δ³⁴S values. The relatively high δ³⁴S values in the Cambrian to Lower Ordovician source rocks are associated with abundant aryl isoprenoids, gammacerane and C₃₅ homohopanes in the extractable organic matter, indicating that these source rocks were deposited in a bottom water euxinic environment with water stratification. Compared with the Upper Ordovician, the Cambrian to Lower Ordovician source rocks show abundance in C₂₈ 20R sterane, C₂₃ tricyclic terpanes, 4,23,24-trimethyl triaromatic dinosteroids and depletion in C₂₄ tetracyclic terpane, C₂₉ hopane. Thus, δ³⁴S values and biomarkers of source rock organic matter can be used for distinguishing the Cambrian and Upper Ordovician source rocks in the Tarim Basin.