Catalytic function of avian cytochrome P450 1A4 and 1A5 (CYP1A4 and CYP1A5) enzymes heterologously expressed using in vitro yeast system

The present study clarifies the enzymatic properties of two avian cytochrome P4501A (CYP1A) paralogs, CYP1A4 and 1A5, using a yeast-based vector system. Recombinant CYP1A4 and 1A5 proteins from common cormorant (Phalacrocorax carbo) were expressed in yeast cells, and showed typical reduced CO-difference spectra with a peak at 446 nm. Kinetic analysis of O-dealkylase of methoxy-, ethoxy-, pentoxy- and benzyloxyresorufin catalyzed by the CYP1A enzymes revealed that Vmax value for ethoxyresorufin-O-deethylase (EROD) activity was much higher than that for the other three O-dealkylase activities for both isozymes. Interestingly, remarkable substrate specificity of the CYP1As was observed for O-dealkylation of benzyloxyresorufin and methoxyresorufin; CYP1A4 was highly specific for catalyzing benzyloxyresorufin-O-debenzylase activity, whereas CYP1A5 was more efficient in catalyzing methoxyresorufin-O-demethylase activity. The present study also measured CYP1A-dependent EROD activity in the presence of 2,3,7,8-tetrachlorodibenzofuran (TCDF) to evaluate the ability of this dioxin-like congener to inhibit the EROD activity. One hundred nanomolar TCDF noncompetitively inhibited CYP1A5-dependent EROD activity, although no inhibitory effect was detected for CYP1A4-dependent EROD activity. These results indicate that the avian CYP1A paralogs have different affinities for substrate and inhibitor, thus suggesting their distinct physiological and toxicological roles.     

Further Occurrence of Brown Ores in Kuroko-type Deposits in Japan

Abstract: The occurrence of so-called brown ore from the Kuroko-type deposits in Japan was examined. Brown ore specimens from the Kannondo, Inarizawa, Matsumine, Fukazawa, Uchinotai, Kosaka (orebody unknown) and Nurukawa deposits have been found in the ore collection stored by Dowa Mining Co. Ltd. and the subsidiary companies. In addition, occurrences from the Fukazawa, Matsumine, Ezuri, Shakanai, and Ginzan deposits were previously reported. The brown ore is characterized by its color and by its higher Ag concentration (up to around 2,400 g/t) than ordinary black ores. This type of ore occurs commonly in the Kuroko-type deposits in Japan, whereas its extent is limited. The brown ore is a type of Au-rich massive sulfide ore formed in submarine hydrothermal system.     

Sulfur Isotope Study on Hg and Sb Deposits in Japan

Abstract. Sulfur isotope ratios of cinnabar from Hg deposits and stibnite, jamesonite and berthierite from Sb deposits in Japan are examined in order to understand metallogeneses of Hg and Sb deposits in Japanese island arcs. The studied Hg and Sb deposits include the Hg deposit at Yamato‐suigin (Honshu) and the Sb deposit at Ichinokawa (Shikoku) in the Southwest Japan arc. In addition, Hg deposits including Itomuka and Ryushoden in central Hokkaido and Hg and Sb mineralizations in Northeast Japan arc are examined. The δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, including the Itomuka and Ryushoden deposits range widely, from ‐10 to +16 %o, the highest values encountered at the Samani deposit. The δ³⁴S values of cinnabar from other areas in Japan range from ‐12 to +5 %o, having δ³⁴S values higher than +2 %o from southwestern Hokkaido (Meiji deposit), Shikoku (Suii deposit) and Kyushu (Hasami and Yamagano deposits). On the other hand, the δ³⁴S values of stibnite from all areas in Japan range from ‐14 to +5 %o, having positive δ³⁴S values higher than +2 %o up to +5 %o from southwestern Hokkaido (Yakumo, Toyotomi and Teine deposits) and eastern‐central Honshu (Hachiman and Daikoku deposits). The variation in δ³⁴S values of Hg and Sb deposits may reflect the variation in δ³⁴S values of country rocks or variation in mixing ratio of sulfur extracted from the country rocks, sulfur derived from seawater sulfate, and sulfur derived from magmatic emanations. The relatively high δ³⁴S values of cinnabar and stibnite higher than +2 %o from southwestern Hokkaido, eastern‐central Honshu and Kyushu are probably caused by contribution of volcanic emanation from arc magmas having positive σδ³⁴S values, whereas the positive δ³⁴S values of cinnabar higher than +2 %o from Suii deposit in Shikoku may be attributed to structurally substituted sulfate in limestone country rocks and/or sulfur derived from seawater sulfate. However, the wide range of the δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, is difficult to explain at this moment. Other relatively low, negative δ³⁴S values of cinnabar and stibnite, berthierite from other areas in Japan may be attributed to 1) incorporation of isotopically light sedimentary sulfur or sulfur derived from ilmenite‐series silicic magma, or 2) less contribution of volcanic emanation from arc magmas having positive σδ³⁴S values.     

Origin of Ore-forming Fluids Responsible for Gold Mineralization of the Pongkor Au-Ag Deposit, West Java, Indonesia: Evidence from Mineralogic, Fluid Inclusion Microthermometry and Stable Isotope Study of the Ciurug–Cikoret Veins

The Pongkor gold–silver mine is situated at the northeastern flank of the Bayah dome, which is a product of volcanism in the Sunda–Banda Arc. The hydrothermal alteration minerals in the Ciurug–Cikoret area are typical of those formed from acid to near‐neutral pH thermal waters. On the surface, illite/smectite mixed layer mineral (I/Sm), smectite and kaolinite, and spotting illite, I/Sm and K‐feldspar alteration occur at the top of the mineralized zone. Silicification, K‐feldspar and I/Sm zones are commonly formed in the wall rock, and gradually grade outwards into a propylitic zone. The mineralization of precious metal ore zone is constrained by fluid temperatures between 180 and 220°C, and with low salinity (<0.2 wt% NaCl equivalent) and boiling condition. The minimum depth of vein formation below the paleo‐water table is approximately 90–130 m for the hydrostatic column. Hydrogen and oxygen isotope data for quartz and calcite show relatively homogeneous fluid composition (?53 to ?68‰δD and ?5.7 to +0.3‰δ¹⁸O H₂O). There is no specific trend in the data with respect to the mineralization stages and elevation, which suggests that the ore‐forming fluids did not significantly change spatially during the vein formation. The stable isotope data indicate mixing between the hydrothermal fluids and meteoric water and interaction between the hydrothermal fluids and the host rock.     

Textural and Chemical Evolution of Unidirectional Solidification Textures in Highly Differentiated Granitic Rocks at Kharaatyagaan,Central Mongolia

Unidirectional solidification texture (UST) in an aplite body is recognized in the Neoproterozoic highly differentiated granitic rocks at Kharaatyagaan, central Mongolia. On the basis of crystal morphology, two main types of UST were identified in the aplite body: (i) thin crenulate UST layers; and (ii) thick intergrowth UST layers. Bulk geochemistry indicates that the Kharaatyagaan UST‐bearing aplite and aplite dike are alkaline, and are enriched in light rare‐earth elements. Scanning electron microscopy and cathadoluminescence imaging of UST quartz from Kharaatyagaan show four types of quartz: euhedral quartz phenocrysts with well‐developed concentric growth zoning (Qa1) in the aplite; euhedral quartz with weak growth zoning in the aplite (Qa2); UST quartz exhibiting distinct growth zones (Qu1); and UST quartz showing mosaic texture (Qu2). Crystallization temperatures determined by the Ti‐in‐quartz geothermometer of Qa1 and Qu1 quartz range between around 500°C and 780°C and Qa2 and Qu2 range between about 490° and 630°C. The cathodoluminescence textures of quartz are predominantly caused by variations in the trace elements contents of quartz. The Qa1 and Qu1 quartz crystals are characterized by high Ti and Al concentrations in the quartz lattice, and are observed in the bottom of the Kharaatyagaan hill, which formed in the early, less evolved magmatic stage. The Qa2 and Qu2 UST quartz characterized by low Ti and variable Al concentrations are found at the top. The UST layers crystallized along the upper part of the magma chamber in the presence of fluid phases exsolved from felsic magma.     

Characteristics of Gold Mineralization at the Ciurug Vein, Pongkor Gold-Silver Deposit, West Java, Indonesia

Abstract. The Pongkor Gold‐Silver Mine, Bogor district, West Java, is approximately 80 km southwest of Jakarta. The gold and silver mineralization in the area is present in a deposit consisting of an epithermal vein‐system named individually as the Pasir Jawa, Gudang Handak, Ciguha, Pamoyanan, Kubang Cicau, and Ciurug veins. In the area studied, rocks of basaltic‐andesitic composition are dominated by volcanic breccia and lapilli tuff, with andesite lava and siltstone present locally. The hydrothermal alteration minerals in the Ciurug area are typical of those formed from acid to near‐neutral pH thermal waters, where the acid alteration is distributed from the surface to shallow depth, while the near‐neutral pH alteration becomes dominant at depths. The Ciurug vein shows four main mineralization stages where each discrete stage is characterized by a specific facies; these are, from early to late: carbonate‐quartz, manganese carbonate‐quartz, banded‐massive quartz and gray sulfide‐quartz facies. The major metallic minerals are pyrite, sphalerite, chalcopyrite and galena; they occur in almost each mineralization stage. Bornite was observed only in the southern part of the Ciurug vein at a depth of 515 m, and the occurrence of this mineral is reported here for the first time. Electrum and silver sulfides (mostly acanthite) are minor, whereas silver sulfosalts, stromeyerite and mckinstryite, and covellite are in trace amounts. The silver sulfosalts have compositional ranges of pearceite, antimon‐pearceite and polybasite. Most of the electrum occurs coexisting with other sulfide minerals, as inclusions in pyrite grains, with very little as inclusions in chalcopyrite or sphalerite. Gold grades within the Ciurug vein vary from 1.2 to hundreds of ppm, where the highest gold grade occurs in the latest mineralization stage in a thin sulfide band in vein quartz. Fluid inclusion microthermometry of calcite and quartz indicates deposition throughout the mineralized veins in the range from 170 to 230d?C and from low salinity fluids (predominantly lower than 0.2 wt% NaCl equiv.). Fluid inclusions occur with features of boiling.     

Petrological and Geochemical Characteristics of Intrusive Rocks Related to Porphyry Copper Mineralization and the Implications for the Genesis of Deposits in the Namosi area, Viti Levu, Republic of the Fiji Islands

In the Namosi district, of Viti Levu Island, Republic of the Fiji Islands, we conducted chemical analysis on intrusive rocks and attempted to clarify the relationship between petrological characteristics and mineralization. Samples were collected from the Waisoi copper deposit, Waivaka corridor, Waisomo, Wailutelevu and Wainabama Southwest localities. The intrusive rocks in the district show the overall characteristics of calc-alkaline magnetite series. Using the normative composition diagram for granite classification, most of the intrusive rocks plot in the tonalite, granodiorite, quartz monzodiorite and quartz diorite fields. Rare earth element (REE) analysis revealed that at Waisoi the intrusive rocks tend towards an Eu positive anomaly, whereas most of those at Waisomo tend to have a negative anomaly. The (Ce_cn/Yb_cn)/Yb_cn ratio shows that the intrusive rocks in the Namosi district may be derived from a mantle origin magma possibly contaminated by crustal materials. Waisoi rocks have less contamination with continental crust and show higher gold content compared to those of the Waivaka corridor. The observed differences between Waisoi and Waivaka corridor in the Cu/Au ratio might also be caused by varying amounts of contamination by crustal materials. There is no clear correlation between the La/Yb ratio and K–Ar ages, however, the La/Yb ratio of the Waivaka corridor rocks has a wide range, suggesting a variable amount of crustal contamination of the magma from 7 to 5 Ma. The less crustal contamination and generation of relatively high silica contents under relatively oxidized conditions in the Waisoi magmas is correlated with Au-rich porphyry copper mineralization and in contrast more crustal contamination produced Au-poor porphyry copper mineralization at the Waivaka Corridor in the Namosi district.     

Stable isotope and petrologic evidence for open-system degassing during the climactic and pre-climactic eruptions of Mt. Mazama, Crater Lake, Oregon

Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km³ of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H₂O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ³⁴S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ³⁴S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H₂O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ³⁴S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ³⁴S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H₂O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H₂O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ¹⁸O values, have elevated δ³⁴S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ³⁴S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case).     

Size distribution of condensed aromatic rings in various soil humic acids

Condensed aromatic rings are important skeletal components with regard to the recalcitrant nature of humic acids (HAs) in the environment. However, they have not been extensively studied. The relative content and composition (size distribution) of condensed aromatic rings in HAs were obtained from various soils subjected to transmission electron microscopy (TEM) and X-ray diffraction (XRD) profile analysis. In the XRD profiles of all the HAs, the 11 band that was derived from the carbon layer planes was clearly observed. Analysis of the 11 band indicated that the size of the carbon layer planes in HAs ranged from 0.48-1.68 nm, corresponding to 4- to 37-ring condensed aromatic structures. The contents of the total and larger carbon layer planes were larger in HAs with darker color and larger aromatic carbon content. At the same time, the carbon layer planes in HAs were smaller than those in a carbon black reference (from 0.24 to >3.66 nm). In the TEM analysis, fringes observed in HAs were less distinct and less ordered than those in carbon black, which was in agreement with the XRD result.     

Concentration of Gold(I) Thiosulfate Complex Ions on the Surface of Alumina Gel and their Change in Chemical State: Preliminary Experiment in the Elucidation of the Formation Mechanism of Epithermal Gold Deposits

In order to elucidate the formation mechanism of low‐sulfidation epithermal gold deposit, the adsorption of [Au(S₂O₃)₂]^3? (a model compound for gold(I) complex ion) on alumina gel (a model compound for the aluminum‐bearing minerals) and change in chemical state of [Au(S₂O₃)₂]^3? after adsorption on the surface of alumina gel were investigated as a basic model experiment. In the pH range from 4 to 6, the amount of [Au(S₂O₃)₂]^3? adsorbed on alumina gel decreased with increasing pH and decreased drastically between pH 6 and 7, and then approached zero above pH 8 at 30°C. At 60°C, the amount of gold adsorbed above pH 7 was enhanced compared with that at 30°C. This adsorption tendency indicates that [Au(S₂O₃)₂]^3? is mainly adsorbed by electrostatic interaction between negative charges of [Au(S₂O₃)₂]^3? and positive charges of alumina gel because of its isoelectric point around pH 9. The chemical state of gold after adsorption of [Au(S₂O₃)₂]^3? on alumina gel was examined using X‐ray absorption near edge structure (XANES). The result showed that [Au(S₂O₃)₂]^3? was spontaneously reduced to elemental gold even in the absence of specific reducing agents after adsorption on alumina gel. This reduction reaction might occur by two steps: (i) disproportionation of the adsorbed [Au(S₂O₃)₂]^3? at the surface of alumina gel, and (ii) spontaneous reduction of the resulting gold(III) complex ions on the surface of alumina gel. The experimental results suggest that aluminum plays an important role in the concentration of gold(I) complex ions and subsequent reduction of gold during the formation of low‐sulfidation epithermal gold deposits.