Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater. Mg isotopes are significantly (up to 5‰) fractionated during carbonate precipitation by preferential incorporation of ²⁴Mg, while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of ²⁶Mg. Thus, the marine Mg cycle could be reflected by seawater Mg isotopic composition (δ²⁶Mg_sw), which might be recorded in marine carbonate. However, carbonates are both texturally and compositionally heterogeneous, and it is unclear which carbonate component is the most reliable for reconstructing δ²⁶Mg_sw. In this study, we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China. Based on petrographic studies, four carbonate components were recognized: micrite, marine cement, brachiopod shell, and mixture. The four components had distinct δ²⁶Mg: (1) micrite samples ranged from ?2.86‰ to ?2.97‰; (2) pure marine cements varied from ?3.40‰ to ?3.54‰, while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range (?3.27‰ to ?3.75‰); (3) values for the mixture component were ?3.17‰ and ?3.49‰; and (4) brachiopod shells ranged from ?2.20‰ to ?3.07‰, with the thickened hinge area enriched in ²⁴Mg. Due to having multiple carbonate sources, neither the micrite nor the mixture component could be used to reconstruct δ²⁶Mg_sw. In addition, the marine cement was homogenous in Mg isotopes, but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ²⁶Mg_sw. Furthermore, brachiopod shells had heterogeneous C and Mg isotopes, suggesting a significant vital effect during growth. Overall, the heterogeneous δ²⁶Mg of the Huangjin limestone makes it difficult to reconstruct δ²⁶Mg_sw using bulk carbonate/calcareous sediments. Finally, δ²⁶Mg_sw was only slightly affected by the faunal composition of carbonate-secreting organisms, even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range (0.2‰–4.8‰) of fractionation during biogenic carbonate formation.     

Rare elements and Nd and Sr isotopic composition in micronodules from the Brazil Basin,Atlantic Ocean

The Sr isotope stratigraphy of the biogenic apatite was used to determine the age of pelagic sediments in the Brazil Basin (Station 1541) that contain ferromanganese micronodules, nodules, and coatings on the weathered volcanic rocks. The age of sediments at horizons 0–5 and 86–90 cm was estimated at 24.1 ± 0.2 Ma and 24.8 ± 0.2 Ma, respectively. The average sedimentation rate in the Late Oligocene was about 13 mm/ka. The hydrogenous Fe–Mn nodule on the sediment surface with the Mn/Fe value of 1.05–1.95 was formed at a rate of 1.2–2.4 mm/Ma, which is 1000 times lower than the growth rate of buried nodule (Mn/Fe 0.4) at depth of 83 cm. Diagenesis provoked changes in the mineral composition of the buried nodule (asbolane-buserite partially replaced by goethite), leading to the loss of a part of Mn, Ni, Li, and Tl but accumulation of trace elements linked with iron oxyhydroxides (Ce, Th, Be, As, and V) were retained. The composition of manganese micronodules at two studied depths in sediments evolved in the course of two stages of ore formation: related to the oxic and suboxic diagenesis. The Sr isotopic composition in manganese micronodules from both horizons do not differ from that of dissolved Sr in the ocean water. The ¹⁴³Nd/¹⁴⁴Nd ratio, which reflects the Nd isotopic composition in the paleocean during the micronodule formation, varies in manganese micronodules from different horizons and is constant in different size fractions.     

Geology and C-O isotope geochemistry of carbonate-hosted Pb-Zn deposits, NW Guizhou Province, SW China

The Pb-Zn metallogenic district in NW Guizhou Province is an important part of the Yun-nan-Sichuan-Guizhou Pb-Zn metallogenic province, and also is one of the most important Pb-Zn producers in China. The hosting rocks of the Pb-Zn deposits are Devonian to Permian carbonate rocks, and the basement rocks are meta-sedimentary and igneous rocks of the Proterozoic Kunyang and Huili groups. The ore minerals are composed of sphalerite, galena and pyrite, and the gangue minerals are include calcite and dolomite. Geology and C-O isotope of these deposits were studied in this paper. The results show that δ13C and δ18O values of hydrothermal calcite, altered wall rocks-dolostone, sedimentary calcite and hosting carbonate rocks range from -5.3‰ to -0.6 ‰ (mean -3.4‰) and +11.3‰ to +20.9 ‰ (mean +17.2‰), -3.0‰ to +0.9 ‰ (mean -1.3‰) and +17.0‰ to +20.8‰ (mean +19.7‰), +0.6‰ to +2.5 ‰ (mean +1.4‰) and +23.4‰ to +26.5 ‰ (mean +24.6‰), and -1.8‰ to +3.9‰ (mean +0.7‰) and +21.0‰ to +26.8‰ (mean +22.9‰), respectively, implying that CO2 in the ore-forming fluids was mainly a result of dissolution of Devonian and Carboniferous carbonate rocks. However, it is difficult to evaluate the contribution of sediment de-hydroxylation. Based on the integrated analysis of geology, C and O isotopes, it is believed that the ore-forming fluids of these carbonate-hosted Pb-Zn deposits in this area were derived from multiple sources, including hosting carbonate rocks, Devonian to Permian sedimentary rocks and basement rocks (the Kun-yang and Huili groups). Therefore, the fluids mixing is the main precipitation mechanism of the Pb-Zn deposit in this province.     

Carbonate alteration of ophiolitic rocks in the Arabian–Nubian Shield of Egypt: sources and compositions of the carbonating fluid and implications for the formation of Au deposits

Ultramafic portions of ophiolitic fragments in the Arabian–Nubian Shield (ANS) show pervasive carbonate alteration forming various degrees of carbonated serpentinites and listvenitic rocks. Notwithstanding the extent of the alteration, little is known about the processes that caused it, the source of the CO₂ or the conditions of alteration. This study investigates the mineralogy, stable (O, C) and radiogenic (Sr) isotope composition, and geochemistry of suites of variably carbonate altered ultramafics from the Meatiq area of the Central Eastern Desert (CED) of Egypt. The samples investigated include least-altered lizardite (Lz) serpentinites, antigorite (Atg) serpentinites and listvenitic rocks with associated carbonate and quartz veins. The C, O and Sr isotopes of the vein samples cluster between ?8.1‰ and ?6.8‰ for δ¹³C, +6.4‰ and +10.5‰ for δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr of 0.7028–0.70344, and plot within the depleted mantle compositional field. The serpentinites isotopic compositions plot on a mixing trend between the depleted-mantle and sedimentary carbonate fields. The carbonate veins contain abundant carbonic (CO₂±CH₄±N₂) and aqueous-carbonic (H₂O-NaCl-CO₂±CH₄±N₂) low salinity fluid, with trapping conditions of 270–300°C and 0.7–1.1 kbar. The serpentinites are enriched in Au, As, S and other fluid-mobile elements relative to primitive and depleted mantle. The extensively carbonated Atg-serpentinites contain significantly lower concentrations of these elements than the Lz-serpentinites suggesting that they were depleted during carbonate alteration. Fluid inclusion and stable isotope compositions of Au deposits in the CED are similar to those from the carbonate veins investigated in the study and we suggest that carbonation of ANS ophiolitic rocks due to influx of mantle-derived CO₂-bearing fluids caused break down of Au-bearing minerals such as pentlandite, releasing Au and S to the hydrothermal fluids that later formed the Au-deposits. This is the first time that gold has been observed to be remobilized from rocks during the lizardite–antigorite transition.     

Carbon isotope composition of sedimentary rocks in the southern Siberian Platform and surrounding fold systems

Organic carbon isotope composition was studied in the sedimentary cover of the southern Siberian Platform and its surrounding fold systems. The rocks experienced catagenesis, metamorphism, and metasomatism. The chloroform bitumoid (CB) has a stable carbon isotope composition within a wide range of postsedimentation transformations. The average values of δ¹³C in CB of the sedimentary cover are ?29.5‰. Metamorphism and, especially, ore metasomatism, at the Sukhoi Log deposit caused a 2‰ increase in the heavy carbon isotope concentration of CB as compared to that of the platform deposits. The narrow variations in carbon isotope composition of the bitumoid are defined by their derivation from lipids, whose components are almost insusceptible to changes in the PT conditions. Kerogen from platform deposits is more strongly depleted than CB in the heavy carbon isotope (δ¹³C_av ? 32.2‰). The insoluble carbonaceous matter (ICM) of the metamorphic shales is significantly enriched in the heavy carbon isotope (δ¹³C_av ? 21.9‰). The highest changes in carbon isotope composition were found in concentrates of ICM from metasomatically altered rocks of the Sukhoi Log deposit (δ¹³C_av ? 17.5‰). The heavier carbon isotope composition caused by metamorphism and metasomatism is evidently defined by isotopic exchange between the carbonate carbon and CO₂ of metasomatic solutions, on one hand, and ICM of shales, on the other.     

The oxygen and carbon isotope composition of Carboniferous fossil components: sea-water effects

The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ¹⁸O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ¹⁸O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ¹⁸O and δ¹³C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ¹⁸O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ¹³C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

震旦纪地层黄铁矿硫同位素组成时－空变化特征及扬子地块与晚元古超大陆关系的论证

 扬子地区早震旦世时期沉积岩黄铁矿具有重的硫同位素组成,其δ¹⁴S值从早震旦世椿木组地层的24‰左右逐渐变得更正。在早震旦世扬子地区广泛沉积碳酸锰矿和黑色页岩的民乐组时期达到极正值+60‰,然后又降低至+16‰-+20‰。上述硫同位素组成的时-空变化特征支持了扬子地块属晚元古Rodinia超大陆的一个组成部分的假设。从晚震旦世早期陡山沱组底部开始,沉积岩中黄铁矿硫同位素的δ¹⁴SS出现负值,并继续降低至-27‰以下。早震旦世晚期-晚震旦世早期沉积岩中硫同位素组成特征反映了沉积盆地古海洋环境的剧烈变化,它与大约7亿年时Rodinia超大陆的解体以及扬子地块与其它大陆分离的地质推测相吻合。     

Sulphur- and lead-isotope geochemistry of the Arapuçandere lead–zinc–copper deposit,Biga Peninsula,northwest Turkey

The Arapuçandere Pb–Zn–Cu ore body is a typical vein-type lead–zinc deposit of the Biga Peninsula, and is currently being mined for lead and zinc. In the study area, Permian–Triassic metamorphic rocks, Triassic metaclastic and metabasic rocks, Oligocene–Miocene granitoids, Miocene volcanic rocks, and Quaternary terrigenous sediments crop out. The ore deposits developed as Pb–Zn–Cu-bearing veins along faults in Triassic metasandstone and metadiabase. Microscopic studies reveal that the veins contain galena, sphalerite, chalcopyrite, pyrite, marcasite, covellite, and specular hematite as ore minerals, and quartz, calcite, and barite as gangue minerals. Analysed sulphur-isotope compositions (δ³⁴S_VCDT) of galena, sphalerite, and chalcopyrite range from ? 5.9 to ? 1.9‰ (average ? 3.4‰), from ? 5.5 to ? 1.7‰ (average ? 4.2 ‰), and from ? 3.5 to ? 0.9‰ (average ? 2.6‰), respectively; that of H₂S in the hydrothermal fluid was in the calculated range of ? 5.8 to +0.1‰ (average ? 2.5‰). These isotopic values suggest that magmatic sulphur dominates in sulphides, mixed with minor, isotopically light sulphur. Because no contemporaneous magmatic activity is associated with mineralization, it may be assumed that sulphur was leached from the surrounding Triassic units, mainly from metabasic, partly from metaclastic rocks. Lead-isotope studies indicate a model age of 114–63 Ma for the lead reservoir, in accord with possible sulphur-bearing local source rocks. Thus, the sulphur and lead deposited in the studied ore veins were probably leached from Triassic metabasic and metaclastic rocks some time during the Early Cretaceous to the Palaeocene.     

2.0 Ga orogenic graphite deposits and associated 13C-enriched meta-carbonate rocks from South China Craton: Implications for global Lomagundi event

The Lomagundi (-Jatuli) event, characterized by extremely high positive global inorganic carbon isotope excursion at about 2.2 billion years ago, is pivotal in investigating the causes and consequences of great oxygenation event, inventory and sequestration of carbon on the Earth’s surface, evolution of life, and more profoundly tectonic control on Earth’s environment. However, the reasons that caused the isotopic excursion are not resolved yet. Herein, we report the discovery of meta-carbonate rocks with distinct positive carbon isotopic excursion from the Paleoproterozoic continental collision zone of the Kongling Complex, South China Craton. The δ¹³C_V-PDB values for meta-carbonate rocks show positive values in the range from +5.5‰ to +11.6‰, whereas the δ¹³C_V-PDB values of associated graphite deposits range from ?25.8‰ to ?9.5‰. Zircon U-Pb-Hf isotopes from zircon-bearing meta-carbonate sample yielded weighted average ²⁰⁷Pb/²⁰⁶Pb age of 2001.3 ± 9.5 Ma, with corresponding ε_Hf(t) range from ?7.05 to ?3.16, comparable to the values of local 2.9–2.6 Ga basement rocks. Geochemical characteristics of meta-carbonate rocks, such as their rare earth element patterns and the trace element parameters of La, Ce, Eu, and Gd anomalies and Y/Ho ratio, suggest that the carbonate deposition took place in passive continental margin in association with large volumes of organic carbon. The extensive graphite deposits from Kongling Complex in South China Craton, their equivalents in the North China Craton and elsewhere across the globe prove that the burial of ¹²C-enriched organic carbon has eventually resulted in the global enrichment of ¹³C in the atmospheric CO₂, which is recorded in the marine carbonate rocks. Isotopic mass balance estimates indicate that more than half of the organic carbon was buried during the oceanic closure. Hence, the observed global shift could be directly related to the continent collision event in greater China, thus resolving the long-standing paradox of the Lomagundi global positive carbon isotope excursion. Moreover, the present results suggest that orogenesis play a significant role in sequestration of carbon into the continental crust.     

Mineralogy and Geochemistry of Sedimentary Huntite Deposits in the Egirdir-Hoyran Lake Basin of Southern Turkey

The sediment-hosted huntite-magnesite deposits are located in the Egirdir-Hoyran lake basin in the Isparta Angle (southern Turkey). The deposits occur at two different localities in the region: (1) Kemersirti huntite deposit, (2) Köytepe huntite-magnesite deposit. The huntite-magnesite occurrences are found in shallow lacustrine rocks of the Miocene-Pliocene Kizilcik Formation and formed as a result of Neogene tectonic activity. Based on X-ray diffraction and scanning electron microscopic studies, the mineral assemblage of huntite deposits contains mostly huntite, less magnesite, dolomite, very little calcite, illite, simectite, brucite, and quartz in the Kemersirti area but contain huntite, magnesite, dolomite, and calcite in the Köytepe area.In the huntite and magnesite-bearing huntite samples, MgO varies from 32.70 to 37.95 wt. %, CaO from 7.83 to 15.10 w.t. %, and SiO₂ from 0.99 to 10.60 w.t. %. Ba and Sr are dominant minor elements in the deposits. Ba and Sr for huntite and magnesite bearing huntite in the study area vary from 11 to 233 ppm and from 325 to 765 ppm, respectively. As, U, Zr, V and Ce contents ranged from 11.5-146 ppm, 0.5-3.7 ppm, 1.4-13.2 ppm, 7-34 ppm, and 0.9-2.7 ppm respectively. The huntite-magnesite is characterized by relatively lower Ni (0.5-2.4 ppm) and Co (0.5-1.1 ppm) contents. The huntite and magnesite-bearing huntite occurrences have higher Ba, Sr, As, Zr, V, and U contents than those of the other elements. The d13C isotope values vary between 7.8‰ to 8.8‰ PDB for huntite+magnesite, 8.2‰ PDB for huntite, 1.4‰ PDB for magnesite+dolomite, and 4.0‰ PDB for limestone from deposits in the study area. The δ¹⁸O isotope values of the huntite deposits ranged from 30.4 to 35.5‰ SMOW for huntite+magnesite, 32.4‰ SMOW for huntite, 29.8‰ SMOW for magnesite+ dolomite, and 26.9‰ SMOW for limestone.The presence of nodular huntite and the abundance of gastropod, ostracoda and Chura shells in the carbonate units indicate that the huntite occurrences are precipitated at shallow, alkaline (8.5-9.5 pH) and lower temperature (approximately 25°C) lake conditions. The Mg⁺⁺, Ca⁺⁺ and Si⁺⁺ ions for the huntite formation were derived from the surrounding rocks such as ultrabasic rocks, dolomite, dolomitic limestone, and limestone in the Egirdir-Hoyran lake basin. Also, the C isotope ratios indicate that the CO₂ source for the huntite formations results to sedimentary basin from metamorphic CO₂, carbonate rocks, fresh water carbonates, and ground water. The source of oxygen for the huntite formation may come from marine limestone, fresh water carbonates and meteoric water.     

Mixed Oceanic and Freshwater Depositional Conditions for Beachrocks of Northeast Brazil: Evidence from Carbon and Oxygen Isotopes

Holocene beachrocks of Northeast Brazil are composed predominantly of quartz (90%) with minor carbonate fragments (6% algal detritus) and feldspars (4%). The cement shows three textural varieties: (1) calciferous, surrounding siliciclastic grains; (2) micritic, with an acicular fringe; and (3) cryptocrystalline calcite in pores. Sandstone structures and composition show evidence of submerged and low-energy beaches. Cement is formed by ～20 mol% MgCO₃; the δ¹³C in cement ranges from ?1.3‰ to +3.5‰ PDB and δ¹⁸O varies from ?2.1 to +1.2‰_PDB. The cement was precipitated under high CO₂ pressure, as a result of the interaction of CaCO_3^? saturated seawater and nonsaturated groundwater, in a beach environment.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Radiolarian Age of Chert-hosted Bedded Manganese Deposits from the Gen-otani Mine in the Tamba District, Northern Kyoto City, Japan

Abstract. Numerous bedded manganese deposits sporadically distributed throughout the Tamba district, southwestern Japan are intercalated within chert sequence. It is well known that radiolarian remains are commonly included in both bedded manganese deposits and host cherts. The Gen‐otani mine, one of these deposits, is located at Otani, Keihoku‐Shimonaka, northern Kyoto City. Chemical composition and age of the chert sequence at the mine were examined. Mainly according to SiO₂ and MnO contents together with lithology, the chert sequence is divided into three sections; lower massive chert, middle bedded manganese deposit and upper bedded chert sections. Radiolarian faunas consisting of middle Jurassic species such as Eucyrtidiellum unumaense, Dictyomitrella(?) kamoensis, Parvicingula dhimenaensis, Sethocapsa aitai, Sethocapsa kodrai, Transhsuum brevicostatum, Tricolocapsa plicarum, Unuma echinatus and others were extracted from both the middle manganese section and overlying bedded chert of the upper section. This examination reveals that the bedded manganese deposit at the Gen‐otani mine formed until Bajocian to early Bathonian (middle Middle Jurassic) in age.     

Nanhuan manganese deposits within restricted basins of the southeastern Yangtze Platform,China: Constraints from geological and geochemical evidence

The Nanhuan manganese deposits in the southeastern Yangtze Platform occur in the black shale series in the lower part of the Datangpo Formation. In order to constrain the genesis of the deposits, a detailed study was undertaken that involved field observations, major and trace element analyses, organic carbon analyses, and isotope analyses (C, O, S). The major findings are as follows. (1) The ore-bearing rock series, morphology of the ore bodies, and characteristics of ores in several deposits are similar. The ore minerals are rhodochrosite and manganocalcite. The gangue minerals are mainly quartz, feldspar, dolomite, and illite. Minor apatite and bastnaesite occur in the manganese ores. (2) The ores are enriched in Ca and Mg, whereas they are depleted in Si, Al, K, and Ti compared to wall rocks. The ores normalized to average Post-Archean Australian shale (PAAS) are enriched in Co, Mo, and Sr. The chondrite-normalized rare earth element (REE) patterns for ores and wall rocks are between those of typical hydrogenous and hydrothermal type manganese deposits. Additionally, the ores have positive Ce anomalies with an average Ce/Ce* of 1.23 and positive Eu anomalies with an average Eu/Eu* of 1.18 (normalized to PAAS). (3) The average content of organic carbon is 2.21% in the samples, and the average organic carbon isotopic value (δ¹³C_V-PDB) is − 33.44‰. The average inorganic carbon isotopic value (δ¹³C_V-PDB) of carbonates in Gucheng is − 3.07‰, while the values are similar in the other deposits with an average of − 8.36‰. The oxygen isotopic compositions (δ¹⁸O_V-PDB) are similar in different deposits with an average of − 7.72‰. (4) The sulfur isotopic values (δ³⁴S_V-CDT) of pyrite are very high and range from + 37.9‰ to + 62.6‰ (average of 52.7‰), which suggests that the pyrite was formed in restricted basins where sulfate replenishment was limited. The sulfate concentrations in the restricted basins were extremely low and enriched in δ³⁴S, which resulted in the very high δ³⁴S values for the pyrite that formed in the manganese deposits. Therefore, a terrigenous weathering origin for manganese can be excluded; otherwise, the sulfate would have been introduced into the basins together with terrigenous manganese, which would have decreased the δ³⁴S values of pyrites. The manganese, which originated from hydrothermal processes, was enriched in the restricted and anoxic basins, and then, it was oxidized to manganese oxyhydroxide in the overlying oxic waters whereby the products precipitated into the sediments. The manganese oxyhydroxide in the sediment was then reduced to Mn^2 + and released to the pore waters during the process of diagenesis. Some organic carbon was oxidized to CO₃^2 −, which made the depletion of ¹³C in manganese carbonates. Therefore, we suggest that the Nanhuan manganese deposits are hydrothermal–sedimentary/diagenetic type deposits.     

Stable isotopic composition of soil calcite (O,C) and gypsum (S) overlying Cu deposits in the Atacama Desert,Chile: Implications for mineral exploration,salt sources,and paleoenvironmental reconstruction

Soils overlying two porphyry Cu deposits (Spence, Gaby Sur) and the Pampa del Tamarugal, Atacama Desert, Northern Chile were collected in order to investigate the extent to which saline groundwaters influence “soil” chemistry in regions with thick Miocene and younger sediment cover. Soil carbonate (calcite) was analyzed for C and O isotopes and pedogenic gypsum for S isotopes. Soil calcite is present in all soils at the Spence deposit, but increases volumetrically above two fracture zones that cut the Miocene gravels, including gravels that overlie the deposit. The C isotope composition of carbonate from the soils overlying fracture zones is indistinguishable from pedogenic carbonate elsewhere at the Spence deposit; all δ¹³C_VPDB values fall within a narrow range (1.40–4.23‰), consistent with the carbonate having formed in equilibrium with atmospheric CO₂. However, δ¹⁸O_VPDB for carbonate over both fracture zones is statistically different from carbonate elsewhere (average δ¹⁸O_VPDB = 0.82‰ vs. −2.23‰, respectively), suggesting involvement of groundwater in their formation. The composition of soils at the Tamarugal anomaly has been most strongly affected by earthquake-related surface flooding and evaporation of groundwater; δ¹³C_VPDB values (−4.28‰ to −2.04‰) are interpreted to be a mixture of dissolved inorganic C (DIC) from groundwater and atmospheric CO₂. At the Spence deposit, soils only rarely contain sufficient SO₄ for S isotope analysis; the SO₄-bearing soils occur only above the fracture zones in the gravel. Results are uniform (3.7–4.9‰ δ³⁴S_CDT), which is near the middle of the range for SO₄ in groundwater (0.9–7.3‰). Sulfur in soils at the Gaby Sur deposit (3.8–6.1‰ δ³⁴S_CDT) is dominated by gypsum, which primarily occurs on the flanks and tops of hills, suggesting deposition from SO₄-rich fogs. Sulfate in Gaby Sur deposit gypsum is possibly derived by condensation of airborne SO₄ from volcanic SO₂ from the nearby Andes. At the Gaby Sur deposit and Tamarugal anomaly, pedogenic stable isotopes cannot distinguish between S from porphyry or redeposited SO₄ from interior salars.The three sites studied have had different histories of salt accumulation and display variable influence of groundwater, which is interpreted to have been forced to the surface during earthquakes. The clear accumulation of salts associated with fractures at the Spence deposit, and shifts in the isotopic composition of carbonate and sulfate in the fractures despite clear evidence of relatively recent removal of salts indicates that transfer from groundwater is an ongoing process. The interpretation that groundwaters can influence the isotopic composition of pedogenic calcrete and gypsum has important implications for previous studies that have not considered this mechanism.     

The sulfur isotopic composition of sulfides from ores and host rocks of the Upper Kolyma region,Magadan Oblast

More than 200 analyses of the sulfur isotopic composition of sulfides from various terrigenous and intrusive host rocks, metasomatically altered wall rocks, and gold lodes of the Upper Kolyma region are presented. In accessory pyrite of the metaterrigenous rocks, δ³⁴S varies from ?23.1 to +5.7‰ δ³⁴S of pyrite and arsenopyrite from gold-quartz mineralization is within the range ?10.6 to ?0.4‰ and is close to the average δ³⁴S of pyrite from the metaterrigenous rocks (?4.4‰). In the intrusive rocks, δ³⁴S of pyrite varies from ?3.8 to +2.6‰ (+0.7‰, on average) and drastically differs from δ³⁴S of arsenopyrite from postmagmatic gold-rare-metal mineralization (?7.9 to ?2.7‰; ?5.2‰, on average). The comparison of the δ³⁴S of accessory sulfides from the host rocks with δ³⁴S of sulfides from the gold deposits suggests that sulfur mobilized from the terrigenous sequences participated in the hydrothermal process. The results obtained are consistent with the metamorphic model of the formation of gold-quartz deposits in the Upper Kolyma region.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

First Reliable Re–Os Ages of Pyrite and Stable Isotope Compositions of Fe(‐Cu) Deposits in the Hami Region,Eastern Tianshan Orogenic Belt,NW China

The Eastern Tianshan Orogenic Belt (ETOB) in NW China is composed of the Dananhu–Tousuquan arc belt, the Kanggurtag belt, the Aqishan–Yamansu belt and the Central Tianshan belt from north to south. These tectonic belts have formed through arc–continent or arc–arc collisions during the Paleozoic. A number of Fe(‐Cu) deposits in the Aqishan–Yamansu belt, including the Heifengshan, Shuangfengshan and Shaquanzi Fe(‐Cu) deposits, are associated with Carboniferous–Early Permian volcanic rocks and are composed of vein‐type magnetite ores. Metallic minerals are dominated by magnetite and pyrite, with minor chalcopyrite. Calcite, chlorite, and epidote are the dominant gangue minerals. Pyrite separates of ores from those three deposits have relatively high and variable Re contents ranging from 3.7 to 184 ppb. All pyrite separates have very low common Os, allowing us calculation of single mineral model ages for each sample. Pyrite separates from the Heifengshan Fe deposit have an ¹⁸⁷Re–¹⁸⁷Os isochron age of 310 ± 23 Ma (MSWD = 0.04) and a weighted mean model age of 302 ± 5 Ma (MSWD = 0.17). Those from the Shuangfengshan Fe deposit have an isochron age of 295 ± 7 Ma (MSWD = 0.28) and a weighted mean model age of 292 ± 5 Ma (MSWD = 0.33). The Shaquanzi Fe‐Cu deposit has pyrite with an isochron age of 295 ± 7 Ma (MSWD = 0.26) and a weighted mean model age of 295 ± 6 Ma (MSWD = 0.23). Pyrite separates from these Fe(‐Cu) deposits have δ³⁴S_CDT ranging from ?0.41‰ to 4.7‰ except for two outliers. Calcite from the Heifengshan Fe deposit and Shaquanzi Fe‐Cu deposit have similar C and O isotope compositions with δ¹³C_PDB and δ¹⁸O_SMOW ranging from ?5.5‰ to ?1.0‰ and from 10‰ to 12.7‰, respectively. These stable isotopic data suggest that S, C, and O are magmatic‐hydrothermal in origin. The association of low‐Ti magnetite and Fe/Cu‐sulfides resembles those of Iron–Oxide–Copper–Gold (IOCG) deposits elsewhere. Our reliable Re–Os ages of pyrite suggest that the Fe(‐Cu) deposits in the Aqishan–Yamansu belt formed at ～296 Ma, probably in a back‐arc extensional environment.     

A comprehensive approach to the study of methane-seep deposits from the Lincoln Creek Formation, western Washington State, USA

ABSTRACT A comprehensive approach using palaeontology, petrography, stable isotope geochemistry and biomarker analyses was applied to the study of seven small methane‐seep carbonate deposits. These deposits are in the Oligocene part of the Lincoln Creek Formation, exposed along the Canyon and Satsop Rivers in western Washington. Each deposit preserves invertebrate fossils, many representing typical seep biota. Authigenic carbonates with δ¹³C values as low as ?51‰ PDB reveal that the carbon is predominately methane derived. Carbonates contain the irregular isoprenoid hydrocarbons 2,6,11,15‐tetramethylhexadecane (crocetane) and 2,6,10,15,19‐pentamethylicosane (PMI), lipid biomarkers diagnostic for archaea. These lipids are strongly depleted in ¹³C (δ¹³C values as low as ?120‰ PDB), indicating that archaea were involved in the anaerobic oxidation of methane. Small filaments preserved in the carbonate may represent methanotrophic archaea. Archaeal methanogenesis induced the formation of a late diagenetic phase, brownish calcite, consisting of dumbbell‐shaped crystal aggregates that exhibit δ¹³C values as high as +7‰ PDB. Clotted microfabrics of primary origin point to microbial mediation of carbonate precipitation. Downward‐directed carbonate aggregation in the seeps produced inverted stromatactoid cavities. Large filaments, interpreted as green algae based on their size, shape, arrangement and biomarkers, imply that deposition occurred, in places, in water no deeper than 210 m.