Source Diversity of Ore Sulfur from Mesozoic-Cenozoic Mineral Deposits in the Korean Peninsula Region

Abstract: Sulfides from the Daebo Jurassic granitoids and some ore deposits from Korean Peninsula and Sikhote Alin occurring in different basement settings were analyzed for δ³⁴S values. Highly positive values were obtained from Jurassic Mo skarn deposit at Geumseong of the Ogcheon belt (average +13. 0%), Au‐quartz vein deposits at Unsan, North Korea (+6. 7%), and late Paleozoic Sn‐F deposit at Votnesenka (+8. 2%), Khanka massif, Russia. Together with published data of that region, regional variation of δ³⁴S values is shown across Korean Peninsula. Sulfur isotopic data published are compiled on 88 ore deposits, whose mineralization epochs belong to Cretaceous (58 deposits), Jurassic (25 deposits) and Precambrian (4 deposits) in South Korea. Average sulfur isotopic values vary across South Korea as follows: Cretaceous deposits in the Gyeongsang basin, +4. 8% ranging +1.2 ? +12.7‰ (n=28); Jurassic and Cretaceous deposits in the Sobaegsan massif, +3. 5% ranging 0.0 ? +7.8‰ (n=20); those of the Ogcheon belt, +6. 4% ranging ‐0.5 ? +15.4‰(n=19); those of the Gyeonggi massif, +5. 5% ranging +2.1 ? +9.0‰(n = 21). The δ³⁴S values of South Korea tend to be concentrated around +5. 5 permil, exhibiting little, if any, a systematic variation across the geotectonic belts. This tendency is seen also in North Korea and Northeast China within the Cino‐Korean Block, and may be called as Cino‐Korean type. Sulfur of this type is derived mostly from the crystalline basement. Khanka massif of Russia seems to have features of the Cino‐Korean type. In contrast, paired positive/negative belts corresponding to magnetite‐series/ilmenite‐series granitic belts are overwhelming in the Japanese Islands, especially in Southwest Japan. The similar trend is also seen in southern Sikhote Alin and northern Okhotsk Rim, which may be called as Japanese type. Source of the sulfur in this type is likely in the subducting oceanic slab for positive value and accreted sedimentary complex for the negative value, respectively. The Daebo granitoids have an average rock δ³⁴S value of +5. 3 permil, which should have reflected that of the source rocks in the continental crust. The ore sulfur heavier than this value may have been originated in other granitoids having even higher δ³⁴S values, or the ore fluids interacted directly with sulfate sulfur of the host evaporites or carbonate rocks. Rock isotopic values of granitoids and basement rocks need to be examined in future from the above point of view in mind.     

Sulfur Isotopic Variation of Yanshanian Magmatic-hydrothermal Deposits in Southern China

Abstract: Sulfur isotope data (δ³⁴S) of sulfides of more than 6700 samples from 157 ore deposits associated with Early and Late Yanshanian granitic and volcanic activities in South China are reviewed and summarized. Averaged δ³⁴S values of individual deposits vary from ‐9. 3 to +20. 6%, and show a normal distribution pattern with the average of +2%. About 88 % of the ore deposits have values within the range, ?2.5 ? +13.6‰, of associated Yanshanian granitoids. There is a temporal‐spatial variation of δ³⁴S values of the ore deposits. However, no clear zonal distribution parallel to geotectonic NNE lineaments was observed. Spatial distribution of ore sulfide δ³⁴S values in most of the NE part of the whole studied area coincides with that of Yanshanian granitoids and volcanic rocks. A downward tendency of the average values in time is: +3. 0% (n=7, J₁) → +1. 6% (n=29, J₂) → +1. 7% (n=68, J₃) → +1. 8% (n=37, K₁) → ?1. 5% (n=16, K₂). There is an “island” of high and variable δ³⁴S values (0? +16.5‰) occurring within a generally low trough zone (?8 ? 0%) of N‐S about 800 km and E‐W 100 to 300 km, bounded by 110°E ? 116°E longitudes and 22°N ? 31°N latitudes. The island occurs at the junction of three tectonic units and a NE‐trending crustal matching line implying a variety of magmatism occurred at the junction. The low trough zone coincides with a low ferric/ferrous ratio zone of Early Yanshanian granitoids, indicating their genetic relationship. Different genetic types of ore deposits show different histogram patterns suggesting different relationships to magmatic rocks and host strata. Granite/greisen/pegmatite type deposits are most closely associated with granitoids, with average ore sul‐fide δ³⁴S values for individual ore deposits ranging between ‐2. 0 and +4. 1%, and an average of +0. 5% (n = 15) close to type meteoric value of 0%. Porphyry‐type deposits have also narrow range of ?2.2 ? + 4.9‰, with an average value of +1. 1% (n = 18). Skarn‐type dominated ore deposits have a nearly normal distribution pattern with an average of +1. 6% (n = 62), ranging from ‐5. 3 to +11. 5%. Volcano‐subvolcanic ore deposits range between ‐3. 1 and +5. 9% with an average of +2. 3% (n = 19). Other types of hydrothermal ore deposits have averaged δ³⁴S values of individual ones from ‐9. 3 to +20. 6%, with average value of +1. 3% (n=43). Vertical and horizontal zonations of δ³⁴S values of ore deposits around their associated granitoid plutons are observed in several localities. Such zonations may be caused by interaction between magma and/or magmatic fluids and host sedimentary rocks, as well as the evolution of physico‐chemical conditions of ore‐forming fluids. Spatial distribution of ore sulfur isotope compositions is also clearly controlled by tectonics and deep faults. Ore sulfur isotope composition is sometimes strongly affected by host sedimentary rocks, especially by evaporite sulfur with much higher δ³⁴S value and partly by biogenic sulfur with low δ³⁴S value. The δ³⁴S values of Yanshanian granitoids are from ‐2. 5 to +13. 6% for both rock samples and pyrite/pyrrhotite separates from granitic rocks, with similar spatial distribution pattern to those of associated ore deposits. The ore deposits associated with ilmenite‐series granitoids have δ³⁴S values ranging between ‐7. 5 and +10. 4% with an average of +1. 0%, while the ore deposits associated with magnetite‐series granitoids ranging between ?8.0 ? +11.5‰ with an average of +1. 1%. δ³⁴S values of ore deposits tend to converge to +3% as the Fe₂O₃/FeO ratio of associated granitoids increases from 0. 45 to 8. 7.     

40Ar/39Ar Ages of the Da Lien Granite Related to the Nui Phao W Mineralization in Northern Vietnam

⁴⁰Ar/³⁹Ar dating was conducted on the Da Lien granite related to greisen‐skarn type polymetallic (W‐CaF₂‐Cu‐Bi‐Au) mineralization in Nui Phao, northern part of Vietnam in the South China Plate. Biotite and muscovite separates from the biotite‐muscovite granite and greisenized granite indicate four plateau ages: 82.2 ± 0.4 Ma, 82.8 ± 0.3 Ma, 81.5 ± 0.3 Ma and 82.5 ± 0.4 Ma. The plateau ages were not significantly influenced by excess ⁴⁰Ar in dated minerals or by loss of radiogenic ⁴⁰Ar due to hydrothermal activities. The results indicate that solidification of granite related to the polymetallic mineralization occurred in the Late Cretaceous between 82.8 Ma and 81.5 Ma.     

Oxygen Isotopic Compositions of the Cape Ashizuri Granitoids in Southwest Japan

Oxygen isotopic composition was determined on representative samples of the Cape Ashizuri plutonic rocks, in order to estimate the genetic background of the biotite granite and alkaline granitoids. The biotite granite (70.1–76.1% SiO₂) ranged from 8.61 to 9.30‰ δ¹⁸O and averaged as 8.9‰ δ¹⁸O (n = 3), which is much smaller than the same Miocene granitoids of the Okueyama (avg. 10.1‰) and Takakumayama (11.6‰) granitic bodies, which are associated with tin mineralization. Among the alkaline granitoids, quartz syenites also have values as low as 7.14–8.70‰, with an average of 8.0‰ (n = 3), and monzonite and gabbro vary from 6.14 to 7.86‰, with an average of 7.0‰ (n = 3). These alkaline granitoids may be lower crustal in origin. The gabbroids containing 12.5% MgO at the maximum with low Sr initial ratio, are considered to be derived from the upper mantle through the fore‐arc tectonic break‐up on the subducting slab.     

Comparative Studies of the Petrochemistry of Sn–W‐Mineralized Granitoids: Continent vs. Island Arc

Granitic rocks obtained during field excursions of the famed mineralized regions of the Erzgebirge, Germany (mainly tin‐bearing), and South China (mainly tungsten‐bearing) have been geochemically analyzed and their results are compared with similar (mainly tungsten‐bearing) granites in the island‐arc setting of Southwest Japan. The studied granitoids all belong to the ilmenite‐series. The collision‐related Erzgebirge granitoids are rich in K₂O and P₂O_5, have high A/CNK ratios (1.11–1.24, i.e. S type), but are also high in Ga/Al ratio (i.e., having some A‐type characteristics). In South China, the Xihuashan granites, in contrast, are very low in P₂O₅, and have A/CNK slightly above 1.0 (1.01–1.05), indicative of I type granites. The (Sn‐) W‐related granites of southwest Japan have similarly low P₂O₅ and A/CNK ratios, indicative also of I‐type. Both in the Xihuashan and southwest Japan, the tungsten‐related granites have high whole‐rock δ¹⁸O values implying involvement of W‐rich crustal rocks. Sn and W contents of the unaltered granites are lowest in the island‐arc setting where the related Sn–W deposits are smallest in size relative to the collision and continental margin settings of the Erzgebirge and South China.     

Origin of the Cenozoic–Mesozoic magnetite-series and ilmenite-series granitoids in East Asia

Among the Phanerozoic granitoids of East Asia, the most prevailing Cenozoic–Mesozoic rocks are reviewed with respect to gabbro/granite ratio, bulk composition of granitoids, redox state, and O- and Sr-isotopic ratios. Quaternary volcanic rocks, ranging from basalt to rhyolite, but typically felsic andesite in terms of bulk composition in island arcs, are oxidized type, possibly due to oxidants from subducting oceanic crust into the source regions. Miocene plutonic rocks in the back-arc of Japan could be a root zone for such volcanism but are more felsic in composition. Cenozoic–Mesozoic plutonic zones are classified by (1) the redox state (magnetite/ilmenite series), and (2) average bulk composition (granodiorite/granite). The granodioritic magnetite series occur with fairly abundant gabbro and diorite in the back-arc of island arcs (Greentuff Belt) and intercontinental rapture zones (Yangtze Block). These rocks are mostly juvenile in terms of the ⁸⁷Sr/⁸⁶SrI and δ¹⁸O values.The granitic magnetite series with some gabbroids occur in rapture zones along the continental coast (Gyeongsang Basin, Fujian Coast) and the back-arc of island arc (Sanin Belt). They were generated mostly in felsic continental crust, with the help of heat and magmas from upper mantle. The generated granitic magmas had little interaction with C- and S-bearing reducing materials, due probably to extensional tectonic settings. The δ¹⁸O value gives narrow ranges but the ⁸⁷Sr/⁸⁶SrI ratio varies greatly depending upon the age and composition of the continental crust. Granitic ilmenite-series are characterized by high δ¹⁸O values, implying much contribution of sediments. The ⁸⁷Sr/⁸⁶SrI ratios are low in island arcs but very high in continental interior settings. Amount of mafic magmas from the upper mantle seems a key to control the composition of granitoid series in island arc settings, while original composition of the protolith may be the key to control granitoid composition in continental interiors.     

Granitoids and Their Magnetic Susceptibility in South Korea

Abstract: Magnetic susceptibility (MS) measurements were carried out for 1,120 samples in the Middle Proterozoic to Early Tertiary granitoids so far recognized in South Korea, and the lateral and spatial variation of their magnetic susceptibility, i.e., content of magnetite, is studied. The Middle Proterozoic two mica granitoids related to cassiterite (Sn) deposits in northeastern part of the Sobaegsan Massif show very low MS (less than 0.3 A‐ 10^‐3 SI unit), and the Permo‐Triassic tonalitic to granodioritic and monzonitic rocks which are barren in mineralization, distributed in the middle part of South Korea also show low MS (less than 1 A‐ 10^‐3 SI unit). On the contrary the Late Triassic to Jurassic granitoids (= Daebo granitoids) which were evolved from tonalite through granodiorite to granite, and are most widely distributed in South Korea, show a wide variation on MS. Particularly in the Andong, Igsan, Gimcheon and Geochang areas, the granitoids which are barren in mineralization, are characterized by high MS (more than 10 A‐ 10^‐3 SI unit). The Chuncheon, Jecheon, Namyang and Geumsan plutons related to molybdenite (Mo) and/or wolframite or scheelite (W), and fluorite (F) mineralizations show a little high MS (more than 3 A‐ 10^‐3 SI unit). However, more than 60% of the Daebo granitoids show low MS (less than 3 A‐ 10^‐3 SI unit) and the rest show a little high MS (more than 3 A‐ 10^‐3 SI unit). Heterogeneous distribution of magnetite content in the Daebo granitoids is considered to reflect heterogeneity of redox state of the source materials for these granitoids. The Cretaceous to Early Tertiary granitoids (= Bulgugsa granitoids) in the Gyeongsang Basin had been generally evolved in the order of tonalite, diorite, granodiorite, granite and alkali‐feldspar granites, which are closely related to base metal ore deposits, and mostly show higher MS (more than 3 A‐ 10^‐3 SI unit) than other granitoids mentioned above, although some exceptions are recognized in highly evolved alkali‐feldspar granites (SiO₂ > 76%). In contrast, as most of the highly oxidized or evolved Cretaceous granitoids distributed in areas other than the Gyeongsang Basin show lower MS than those of the Gyeongsang Basin, and appear to be magnetite free, ilmenite‐series granites, but they might be hematite bearing magnetite‐series granitoids. Highly oxidized nature of the Bulgugsa granitoids may be due to high Fe₂O₃/FeO ratio of the source materials and also high level intrusion style of the granitic magma activities. Most of the granitic rocks of the Middle Proterozoic, Permo‐Triassic and more than 60% of the Late Triassic to Jurassic (Daebo granitoids) belong to ilmenite–series, however less than 40% of the Daebo granitoids and most Cretaceous ones are magnetite–series. Thus, the granitic magma intruded in Korean Peninsula became oxidized while the intrusive ages become younger.     

Chemical Evolution of Zircons in the Paleogene Naegi Granite,Central Japan

The chemical composition of zircons from S‐ and I‐type ilmenite‐series granitic rocks in the Chubu district is summarized based upon recent electron probe microanalysis. Zircons in S‐type Busetsu granite of the Ryoke Metamorphic Belt have a homogeneous composition with minimum impurities, whereas those of I‐type Naegi granite in the non‐metamorphic Sanyo Belt are enriched in Hf, Y, REE, Th and U along the crystal rims. Similar enrichment has been observed in a variety of zircon called Naegite. These minor components are concentrated in the F‐rich fluid phase of residual melts of the Naegi granite magma, and are crystallized in pegmatites during the latest magmatic stage. High values of Nb and Ta in some Naegite reported previously are attributed to micro‐inclusion of fergusonite.     

Granitoid Series and Mineralization in the Circum-Pacific Phanerozoic Granitic Belts

Abstract: Throughout the Phanerozoic Era, magnetite-series and ilmenite-series granitoids are heterogeneously distributed on both sides of the Pacific Ocean. Ilmenite-series granitoids are dominant in the western Pacific rim, while magnetite-series granitoids prediminate in the eastern Pacific orogenic belt. Regional distribution patterns of the two series of paired belt are also recognized differently, implying different tectonic and geochemical settings on both sides of the Pacific Ocean. The differences reflect on the predominance of Sn-W deposits in the western Pacific but sulfide-forming mineral commodities in the eastern Pacific rims. To determine redox state of granitoids is the first step in mineral exploration of granitoid affinity.     

Initial 87Sr/86Sr ratios of plutonic rocks from Japan

Initial ⁸⁷Sr/⁸⁶Sr rations were determined for more than 80 plutonic rocks in Japan. The ⁸⁷Sr/⁸⁶Sr ratios of gabbroic and granitic rocks show no significant difference in plutonic terranes where both rocks occur closely associated, implying a genetic relationship between them (e.g., Green Tuff belt) or reequilibration at deep level (e.g., Ryoke belt). Wherever granitic rocks occur independently from gabbroic rocks, the granites have higher ratios than the gabbros.Initial ⁸⁷Sr/⁸⁶Sr ratios of the granitic rocks are low (<0.706) in Northeast Japan but high (<0.706) in Southwest Japan, the boundary being the Tanakura Tectonic Line. Within Southwest Japan, the ratios are low along the Japan Sea side of the southernmost area. This regional variation is generally correlated with thickness of the continental crust as deduced from the Bouguer anomaly.Initial ⁸⁷Sr/⁸⁶Sr ratios of the granitic rocks vary from 0.7037 to 0.7124. The low group (<0.706) is considered to consist of essentially mantle-derived magmas contaminated by crustal material in lesser but varying degree, because of its geological setting and initial ⁸⁷Sr/⁸⁶Sr values. The high group may have been formed by contamination of a deep-seated magmas by crustal material or by generation of the main part of the magmas within the continental crust. The ratios of individual belts reflect their own history depending upon age and Rb/Sr ratio of the crustal material.Initial ⁸⁷Sr/⁸⁶Sr ratios of granitic rocks are generally low for the magnetite-series but high for the ilmenite-series. Thus, a negative correlation is observed between initial ratios and ³⁴S for most Cretaceous-Paleogene granites. However, Neogene ilmenite-series granites are low in both initial ⁸⁷Sr/⁸⁶Sr and ³⁴S indicating interaction of the granitic magma with young sedimentary rocks enriched in ³²S.