Sulfur Content and Isotopic Ratio of Cambro-Ordovician Carbonate Rocks from South Korea: A Possible Source for Mesozoic Magmatic-hydrothermal Ore Sulfur

Abstract: Carbonate rocks of Cambrian (18 samples) and lower-middle Ordovician (11 samples) ages from South Korea were analyzed for sulfur contents of structurally substituted sulfate (SSS) and sulfides and their δ³⁴S values. The δ³⁴S values of SSS ranging from +25.9 to +45.2 permil, are averaged as +33.6 and +33.5 permil for the Cambrian and Ordovician rocks, respectively, which indicate high δ³⁴S values of the Cambro-Ordovician seawater. The SSS contents in the carbonate rocks are low being 2.9 to 17.3 ppm S (averaged as 7.0 ppm S). Sulfide sulfur, on the contrary, is much abundant containing 3 to 1,880 ppm S and the δ³⁴S values range widely between –17.6 and +31.1 permil. Sulfide sulfur of the studied rocks excluding impure carbonates has an average content of 187 ppm S and δ³⁴S value of +12.8 permil (n=24). The estimated δ³⁴S (sulfate–sulfide) values, which range from 13.8 to 25.4 permil in general with a few exceptions from 36.5 up to 52.3 permil for some impure carbonates, may provide evidence for the persistent oceanic anoxia with its temporary recovery during the Cambro-Ordovician time.
The SSS and sulfide sulfurs have often higher δ³⁴S values than the Mesozoic-Cenozoic ore sulfur (Ishihara et al., 2000). Since carbonate rocks are very reactive with circulating hydrothermal ore solution, high δ³⁴S values of the Korean ore deposits might be caused to some extent by ³⁴S enrichment from the host carbonates, resulting in the low SSS contents observed.     

Cu–Fe Bearing Zinc Sulfide from Laloki Stratabound Massive Sulfide Deposit, Papua New Guinea: Chemical Characterization

Abstract: A strange, unidentified, Cu-Fe bearing zinc sulfide occurs in the Laloki massive sulfide deposit, Papua New Guinea. The mineral is optically uniform in texture but is chemically variable and zoned even within a single grain. Copper contents vary from 0.1 up to 8.85 wt%. Iron reaches 18.31 wt% at maximum and decreases as Cu increases. It is remarkable, however, that the total Fe+Cu remains essentially unchanged between roughly 18 and 20 wt%. Zn and S are least variable, giving 45.85–47.84 wt% and 33.48–34.58 wt%, respectively. Other trace elements such as Cd and Mn are in general less than 0.2 wt%. It is strongly suggested that the mineral in question constitutes a unique Fe-Cu substitutional solid solution series belonging essentially to the Zn–Fe–Cu–S system.
The ideal chemical formula of the solid solution series can well be presented as Zn₁₀(Fe, Cu)₅S₁₅ or Zn₂(Fe, Cu)S₃, where Fe is always greater than Cu. It is intriguing that chalcopyrite blebs are recognizable restrictively only in nearby portions of the Cu-rich end member with the ideal composition close to Zn₁₀Fe₃Cu₂S_15. It has been confirmed by vacuum-sealed heating experiments that this mineral is decomposed to produce chalcopyrite and Fe-bearing normal sphalerite at temperatures below 200C. This would provide another evidence for the existence of such distinct phase as suggested here.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Hong Kong waters: levels, profiles and distribution

Polybrominated diphenyl ethers (PBDEs) and organochlorine compounds (OCs) were determined in the blubber, liver and kidney of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) stranded in Hong Kong coastal waters during 1995–2001. Among the organohalogen compounds analyzed, DDTs were the most dominant contaminants with concentrations ranging from 9.9 to 470 μg/g lipid wt. PBDEs in Hong Kong cetaceans, which are reported for the first time, were detected in all the samples with values ranging from 0.23 to 6.0 μg/g lipid wt., with a predominance of BDE-47. Results from this study suggest PBDEs should be classified as priority pollutants in Asia. Higher concentrations were found in humpback dolphins than in finless porpoises, and this was attributed mainly to differences in habitat. Elevated residues of PCBs and DDTs in some cetaceans suggest these species may be at risk.     

Bayesian and Neural Network Approaches to Estimate Deep Temperature Distribution for Assessing a Supercritical Geothermal System: Evaluation Using a Numerical Model

The temperature distribution at depth is a key variable when assessing the potential of a supercritical geothermal resource as well as a conventional geothermal resource. Data-driven estimation by a machine-learning approach is a promising way to estimate temperature distributions at depth in geothermal fields. In this study, we developed two methodologies—one based on Bayesian estimation and the other on neural networks—to estimate temperature distributions in geothermal fields. These methodologies can be used to supplement existing temperature logs, by estimating temperature distributions in unexplored regions of the subsurface, based on electrical resistivity data, observed geological/mineralogical boundaries, and microseismic observations. We evaluated the accuracy and characteristics of these methodologies using a numerical model of the Kakkonda geothermal field, Japan, where a temperature above 500 °C was observed below a depth of about 3.7 km. When using geological and geophysical knowledge as prior information for the machine learning methods, the results demonstrate that the approaches can provide subsurface temperature estimates that are consistent with the temperature distribution given by the numerical model. Using a numerical model as a benchmark helps to understand the characteristics of the machine learning approaches and may help to identify ways of improving these methods.

     

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.     

Chemistry and Sulfur Isotopes of the Chert-Clastic Sequence Surrounding the Kajika Massive Sulfide Ores at the Ashio Copper Mine, Ashio Terrane, Central Japan

Abstract. Chemical and sulfur isotopic compositions were obtained for a series of rocks within the chert‐clastic sequence surrounding the Kajika massive sulfide ore horizon at Shibukawasawa in the Ashio copper‐mining district, Ashio Terrane, central Japan. The sequence is lithologically classified into three units: chert, siliceous shale with basic volcanics, and sandstone‐shale, in ascending stratigraphic order. The Kajika ore horizon corresponds to the lowermost part of the unit that contains siliceous shale with basic volcanics. The rocks around the Kajika ore horizon are enriched in P₂O₅ (max. 0.22 %), Ba (max. 2400 ppm), Cu (595 ppm), V (323 ppm), Pb (168 ppm), Zn (124 ppm), and Mo (24 ppm) in siliceous shale; and Ba (4220 ppm), Zr (974 ppm), Cr (718 ppm), Ni (492 ppm), V (362 ppm), Zn (232 ppm), Nb (231 ppm), and Co (71 ppm) in the basic volcanics. The siliceous shale is enriched in a number of redox‐sensitive elements such as Cu, V, Pb, Zn, and Mo, which are known to be enriched in black shale and anoxic and hydrothermal sediments. The δ³⁴S values of sulfides in the chert and sandstone‐shale lie in the range of 0±2 %, and those in the siliceous shale range from ‐5 to ‐14 %. The measured δ³⁴S values in the basic volcanics are ‐0.3, ‐2.7, and ‐31.5 %. These heavier δ³⁴S signatures (around 0 %) recorded throughout the sequence indicate that the rocks formed under anoxic bottom‐water conditions. Slightly lighter δ³⁴S values recorded in siliceous shale might reflect significant mixing of sulfides that formed by sulfate‐reducing bacteria in an overlying oxic environment. The long‐term duration of anoxic conditions indicated by the heavier δ³⁴S signature is considered to have played an important role in protecting the Kajika sulfide ores from oxidative decomposition and preserving the ores in sedimentary accumulations.     

Paleoceanography and Heavy Metal Enrichment of Mudstones in the Green Tuff Region, Northeastern Japan

Abstract. A series of mudstones corresponding to N.8 to N.17 of Blow from the Uyashinai Mudstone Member, the Onnagawa Formation and the Funakawa Formation in the Taiheizan area of the central Green Tuff region, northeast Japan, was examined by chemical analysis. According to conventional chemical systematics, the mudstones are analyzed in terms of detrital, biogenic-A (siliceous), biogenic-B (calcareous) and hydrogenous components. The relative contribution of the biogenic-A (siliceous) component increases in upward succession in the Uyashinai and Onnagawa mudstones, whereas the contribution of the biogenic-B (calcareous) component is restricted to the lower Uyashinai mudstones. The contribution of hydrogenous components Zn, Pb, Cu and Ba tends to increase during the Nishikurosawa stage, and decreases near the Nishikurosawa/Onnagawa boundary (Pb and Ba) or in the Onnagawa stage (Zn and Cu). The observed enrichment of heavy metals in the Uyashinai mudstones is attributed to the onset of vigorous upwelling of deep water with higher nutrient and metal content associated with a contemporaneous change in global deep-water circulation.     

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.