Geology, Mineralogy, and Formation Environment of the Disseminated Gold-Silver Telluride Bulawan Deposit, Negros Occidental, Philippines

Abstract: The Bulawan deposit is located in the porphyry copper belt of southwest Negros island, Philippines. Propylitic, K–feldspar, sericitic, and carbonate alteration types can be distinguished in the deposit. Propylite alteration occurs mainly in Cretaceous-Eocene andesitic lavas and agglomerates while K–feldspar, sericite and carbonate alteration types occur mostly in the Middle Miocene dacite porphyry breccia pipes and stocks which were intruded into the andesites. K-feldspar zones occur in the inner parts of the sericitized zone. Sericite alteration overprinted the propylitized and K-feldspar alteration zones, at lower temperature than epidote and chlorite in the propylitized zone. Carbonate alteration is associated with the mineralization in the center of the breccia pipes and along faults. Mineralization consists of gold-silver telluride ores that are hosted by the carbonate– and sericite-altered dacite porphyry breccia pipes. The Bulawan ores occur mainly as disseminations, but unlike many epithermal gold deposits, lack classical epithermal colloform and crustiform quartz veins. The ore minerals are sphalerite, galena, chalcopyrite, pyrite and tetrahedite-tennantite with minor amounts of electrum, calaverite, petzite, sylvanite, hessite, tellurobismuthite, coloradoite, altaite, and rucklidgeite. Electrum and telluride minerals are associated mostly with calcite and dolomite-ankerite minerals. Fluid inclusions in quartz and calcite in clasts of propylitized andesite in the breccia pipes homogenize from about 300° to 400°C while fluid inclusions in quartz, calcite and sphalerite within the dacite porphyry breccia pipes homogenize between 300° to 310°C. The ores were formed around 300°C from hydrothermal solutions with salinity of about 6. 6 wt % NaCl equivalent. The presence of sylvanite and calaverite as intergrowths with each other, and the Ag content of calaverite are consistent with the above temperature estimate. Based on paragenesis, the Bulawan deposit formed in a pyrite-stable environment, with pH between 3. 4 and 5. 5, f_O2 between 10^-32 to 10^-30 atm, f_S2 between 10^-9.8 to 10^-7.8 atm, f_Te2 between 10^-8.9 to 10^-6.5 atm, and total sulfur content about 10^-2.8 molal. The dominant reduced sulfur species in the ore solutions may have been H₂S_(aq), and the likely aqueous tellurium species were H₂Te_(aq) and H₂TeO_3(aq). The ore minerals in the Bulawan deposit were probably formed by mixing of slightly saline and low salinity fluids.     

Polymetallic Mineralization at the Shin-Ohtoyo Deposit, Harukayama District, Hokkaido, Japan

Abstract: The Shin-Ohtoyo Cu–Au deposit is located in the Harukayama district, 20 km west of Sapporo, Hokkaido, Japan. Both acid-type disseminated and adularia–quartz–type vein Au mineralizations have been recognized within a small distance of less than 500 m in the district. Mineralogical characteristics of sulfide ores from the Shin-Ohtoyo deposit have been proved to be polymetallic. Ore minerals containing Sn, V, Bi and Te are recognized. Nine ore types are recognized in terms of characteristic mineral assemblage; (1) chalcedonic quartz veinlets in silicified zone around the deposit, (2) bismuthinite, emplectite, friedrichite and tetrahedrite, (3) an unnamed Cu–Sn–Fe–Zn sulfide, colusite-series minerals, stannoidite, emplectite and tetrahedrite, (4) bournonite, Se-bearing galena and tetrahedrite, (5) luzonite/famatinite and Ag-bearing tetrahedrite, (6) colusite-series minerals, emplectite, aikinite and tetrahedrite/goldfieldite, (7) luzonite/famatinite, colusite-series minerals, mawsonite and tetra–hedrite/goldfieldite, (8) enargite, luzonite/famatinite and tetrahedrite, and (9) colusite-series minerals and tetrahedrite. The first occurrence of friedrichite and stibiocolusite from Japan are reported. The chemical formula of the unnamed phase corresponds to Cu₆(Cu, Fe, Zn)Sn₃S₁₀. Sulfur isotopic ratios (δ³⁴S) of sulfides from the stockpile range from –0. 5% to +1. 9%, and those from drill cores recovered by Metal Mining Agency of Japan (MMAJ) vary from –2. 7% to +0. 8%. Sulfur isotopic ratio of barite in a cavity in the silicified tuff breccia collected from the stock pile yields +27. 1%, while that of barite collected from MMAJ core is +21. 7%. Sulfur isotopic thermometry applied for a pair of barite (+21. 7%) and associated pyrite (+1. 8%) indicates about 300°C. High–Te tetrahedrite composition from both the chalcedonic quartz vein in the silicified zone around the Shin-Ohtoyo deposit and the polymetallic sulfide ores from the adit of the deposit, suggests that the Au mineralization in the former is attributed to a hydrothermal system marginal to the polymetallic mineralization.     

Genesis of the Mamut Porphyry Copper Deposit, Sabah, East Malaysia

Abstract: The Mamut deposit of Sabah, East Malaysia, is a porphyry type Cu‐Au deposit genetically related to a quartz monzonite (“adamellite”) porphyry stock associated with upper Miocene Mount Kinabalu plutonism. The genesis of the Mamut deposit is discussed based on petrology of the intrusives in the Mount Kinabalu area combined with ore– and alteration–petrography, fluid inclusion and sulfur isotope studies. Groundmass of the adamellite porphyry at Mamut is rich in K which suggests vapor transport of alkaline elements during the mineralizing magmatic process, while the groundmass of the post‐ore “granodiorite” porphyry at Mamut contains small amounts of normative corundum suggesting depletion in alkaline elements at the root zone of the magma column. Sub‐dendritic tremolitic amphibole rims on hornblende phenocrysts in the Mamut adamellite porphyry suggest interaction between the mineralizing magma and the exsolved fluids. Occurrences of clinopyroxene microphenocrysts and pseudomor‐phic aggregates of shredded biotite and clinopyroxene after hornblende phenocrysts in the barren intrusives imply lower water fugacity and decreasing in water fugacity, respectively. Compositional gap between the core of hornblende phenocrysts and the tremolitic amphibole rims and those in the groundmass of the Mamut adamellite porphyry suggests a decrease in pressure. Higher X_Mg (=Mg/(Mg+Fe) atomic ratio) in the tremolitic amphibole rims in the Mamut adamellite porphyry compared to those of the barren intrusions suggests high oxygen fugacity. High halogen contents of igneous hydrous minerals such as amphiboles, biotite and apatite in the Mamut adamellite porphyry suggest the existence of highly saline fluids during the intrusion and solidification of the mineralizing magma. Fluid inclusions found in quartz veinlet stockworks are characterized by abundant hypersaline polyphase inclusions associated with subordinate amounts of immiscible gaseous vapor. Both Cu and Au are dispersed in disseminated and quartz stockwork ores. Chalcopyrite and pyrrhotite as well as magnetite are the principal ore minerals in the biotitized disseminated ores. Primary assemblage of intermediate solid solution (iss) and pyrrhotite converted to the present assemblage of chalcopyrite and pyrrhotite during cooling. Subsequent to biotitization, quartz veinlet stockworks formed associated with retrograde chlorite alteration. The Cu‐Fe sul–fides associated with stockwork quartz veinlet are chalcopyrite and pyrite. Overlapping Pb and Zn and subsequent Sb mineralizations were spatially controlled by NNE‐trending fractures accompanying the phyllic and advanced argillic alteration envelope. Sulfur isotopic composition of ore sulfides are homogeneous (about +2%) throughout the mineralization stages. These are identical to those of the magmatic sulfides of Mount Kinabalu adamellitic rocks.     

Metallogenesis of Porphyry Cu Deposits of the Western Luzon Arc, Philippines: K-Ar ages, SO3 Contents of Microphenocrystic Apatite and Significance of Intrusive Rocks

Abstract: K–Ar ages of the following porphyry Cu deposits in the western Luzon arc are determined: Lobo-Boneng (10.50.4 Ma), Santo Niño (9.50.3 Ma), Black Mountain (2.10.1 Ma), Dizon (2.50.2 Ma) and Taysan (7.30.2 Ma). Microphenocrys-tic apatite in the late Cenozoic intermediate to silicic intrusions associated with porphyry Cu deposits in the western Luzon arc contains sulfur as SO₃ detectable by electron probe microanalyzer. Sulfur is supposed to have been accommodated dominantly as oxidized species in oxidizing hydrous magmas that generated porphyry Cu deposits. Likewise, such high SO₃ contents in microphenocrystic apatite are common characteristics of the intermediate to silicic magmatism of the western Luzon arc, from tonalitic rocks of the Luzon Central Cordillera of about 15 Ma to an active magmatism at Mount Pinatubo. Thus, the western Luzon arc has been generating porphyry Cu mineralization associated with oxidizing hydrous intermediate to silicic magmatism related to eastward subduction, since Miocene to the present day. Intermediate to silicic rocks since 15 Ma to present-day western Luzon arc generally show high whole-rock Sr/Y ratio ranging from 20 to 184. However, porphyry Cu deposit is not necessarily related to the rocks that show higher Sr/Y ratios compared to the other barren rocks in the western Luzon arc. The characteristics of the intermediate to silicic magma associated with porphyry Cu deposit are not attributed to the composition of the source material of the magma, but to the properties defined by the high activity of oxidized species of sulfur in the fluid phase that is encountered during the generation of intermediate to silicic magmas.     

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.     

Generation and Evolution of Ore Fluids for Porphyry Cu-Au Mineralization of the Santo Tomas II (Philex) Deposit, Philippines

Abstract: The Santo Tomas II (Philex) deposit is a porphyry Cu‐Au deposit, located in the southern part of the Baguio mineral district, Benguet Province, northern Luzon, Philippines. The Santo Tomas II deposit is associated with an intrusive complex consisting of four rock types that are distinguished based on petrography. They are 1) post‐ore clinopyroxene‐bearing hornblende andesite porphyry, 2) ore‐generating hornblende andesite porphyry, 3) hornblende quartz diorite porphyry and 4) porphyritic hornblende quartz diorite. K‐Ar age of hydrothermal biotitization was estimated to be 1.5±0.4 Ma. A number of intrusive bodies having broadly similar petrography and K‐Ar age occur in the vicinity of the Santo Tomas II deposit, such as at Clifton, Ligay (Binang), Bumolo (Waterhole) and Philex Main Camp areas. The intrusions at the Santo Tomas II deposit and in the vicinity are characterized by high X_Mg (Mg/[Mg+Fe] atomic ratio, about 0.7 or higher) of mafic silicate phenocrysts such as hornblende, and high sulfur contents (> 0.2 wt% as SO₃) in accessory microphenocrystic apatite, suggesting a highly oxidizing condition. Sulfur is accommodated dominantly as oxidized species since the crystallization of phe‐nocrysts. Sub‐dendritic rim of tremolitic amphibole on hornblende phenocryst in the ore‐generating andesite porphyry at the Santo Tomas II deposit suggests interaction of magma and aqueous fluid(s) exsolved due to decompression during intrusion. Dissemination of magnetite is associated with hydrothermal biotitization and is followed by sheeted and stockwork quartz veinlets having silician magnetite and rare titanohematite instead of Cu‐Fe sulfides. The silician magnetite‐rich quartz veinlet was formed at f_O2 near the hematite‐magnetite buffer at nearly magmatic temperature, where sulfur dominantly existed as oxidized species such as SO₂. Chalcopyrite and bornite, which commonly exhibit micrographic texture often accompanying Pd telluride and native gold/Au‐rich electrum, are associated with subsequent anhydrite (‐quartz) veinlets and stringers. Both intermediate solid solution (iss) and bornite solid solution (bnss) are thought to have coprecipitated primarily at above 500°C based on fluid inclusion microthermometry and sulfur isotope thermometry applied for anhydrite and associated chal‐copyrite and bornite. The initial iss is considered to have converted to chalcopyrite partly replacing bnss during cooling. The hypersaline polyphase fluid inclusions abundantly found in the sheeted and stockwork quartz as well as anhydrite veinlets with scarce gaseous inclusions suggest that they have been trapped in the two aqueous fluid immiscible region. The western Luzon arc associated with porphyry Cu mineralization is characterized by oxidized hydrous magmatism and shallow emplacement, and by the source of sulfur enriched in ³⁴S.     

Hydrogen Isotope Study of Fluid Inclusions in Vein Quartz of the Hishikari Gold Deposits, Japan

Abstract: The origin of mineralizing fluids responsible for the Hishikari vein-type epithermal Au deposits was studied on the basis of the hydrogen isotopic ratio (δD) of the inclusion fluid from vein quartz and adularia. The origin of hydrothermal fluids was estimated by combination of the present δ values and the oxygen isotopic ratios (δ¹⁸O) previously reported by Shikazono and Nagayama (1993). The water in the fluid inclusions was extracted by means of decrepitation of quartz at 500°C. Hydrogen was obtained by reduction of the collected water with Zn shot at 450°C. The δD values were determined by mass spectrometer. The δD values of inclusion fluid obtained from quartz range from –61 to –114%. These are significantly lower than the δD value of the thermal water presently venting from the Hishikari deposits and that of local meteoric water. Hydrogen isotopic fractionation between water and amorphous silica, which might have initially precipitated from the hydrothermal fluids at least partly, is not a probable cause of this isotopic depletion, while some water might have been released from the initial hydrous amorphous silica during recrystallization to quartz observed presently. Thus, a part of ore fluids for the Hishikari deposits is supposed to have been originated from the water having anomalous δD values of lower than –100%. Such D depletion cannot be caused by simple oxygen-shift of meteoric water or by contribution of magmatic volatiles. The δD values of water released from the shale samples of the Shimanto–Supergroup, a major host to the Hishikari veins range from –132 to –148%. Therefore, the anomalous δD values of inclusion fluids from some vein quartz and adularia suggest that the water released from hydrous minerals of the sedimentary basement rocks by dehydration or the groundwater isotopically exchanged with sedimentary rocks at elevated temperatures during circulation, partly contributed to the hydrothermal fluids responsible for the Hishikari deposits.     

Determination of Uranium in Thirty-six Geological Reference Samples by Fluorimetry and Extractive Spectrophotometry

The uranium contents of 36 geological reference samples have been determined by fluorimetry after ion-exchange separation, and spectrophotometry using Arsenazo III after solvent extraction with tri-n-octylphosphine oxide. The agreement between present results and published data is generally good. The methods of fluorimetry and spectrophotometry proved very convenient in the determination of uranium in geological materials.     

Determination of Selenium in Twenty-Eight Geological Reference Materials by Atomic Absorption Spectrometry

Twenty-eight geological reference samples have been analysed for selenium using atomic absorption spectrometry with hydride generation and quartz cell atomizer and/or with solvent extraction and carbon tube atomizer. Data are presented for 5 CCRMP, 6 USGS, 3 NBS, 6 NIM and 8 GSJ reference materials.     

Geneses of High Chlorine and Silver–Lead–Zinc–Mineralized Granitoids in Tsushima, Japan

Abstract: Miocene granitoids of the Tsushima Islands have unique characteristics that cannot be seen in other major granitic plutons in the Japanese Islands as follows: (1) They are granitic in composition but contain synplutonic mafic dikes, abundant mafic enclaves, and intermediate facies between granite and mafic enclaves. (2) They are mixture of magnetite‐bearing and –free facies, but generally magnetite‐free in the marginal part. (3) They are high in K₂O content (K₆₅=3. 1) and intermediate in normative corundum (C₆₅=0. 1) and δ¹⁸O value (+9% at SiO₂ 70 %), which may be comparable with those of the Miocene Outer Zone granitoids. (4) Yet the initial Sr ratio is low as 0. 7037. (5) They are high in Cl and S, which occur in fluid inclusions and as pyrrhotite>pyrite, respectively. Two genetic models are considered for the source of the unique granitoid magmas: the continental crust or the upper mantle fertilized with Si, K and ¹⁸O. The latter may be the case for the Tsushima granitoids, because of the low initial Sr ratio. The age of the granitoids (16 Ma) indicates the magmatism related to the opening of the Sea of Japan. It is suggested that both basaltic and granitic magmas were generated in the continental lithosphere under an extensional tectonic setting; the two magmas could have been partly mingled. The mingled magma was originally an oxidized type, but reduced during the emplacement by repeated inflow of S and C‐bearing gases from the pelitic wall rocks. Because of the reduction, SO₃ sulfur is almost nil in the rock‐forming apatite, and most of sulfur remained in fluid phase of the magma as reduced species. Cl content was high in the original magma and concentrated in the fluid phase of the residual system which dissolved silver, lead and zinc metals. Such a fluid migrated into the Taishu fracture systems, as the magma crystallized, and formed the silver–lead–zinc deposits.