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.     

Chemical Profiles across a Jurassic Stratiform Manganese Deposit at Katsuyama in the Mino Terrane of Central Japan: Implications for Depositional Environment, Diagenetic Metal Redistribution and Paleoceanography

Abstract. Inorganic chemical compositions are determined for a series of rocks crossing an Early Jurassic stratiform manganese ore deposit in a chert‐dominant sequence at Katsuyama, in the Mino Terrane of central Japan. The lithology in the vicinity of the manganese ore bed is classified into lower bedded chert, black shale, massive chert, manganese ore and upper bedded chert, in ascending order. The rocks surrounding the manganese deposit are anomalously high in certain elements: Pb (max. 29 ppm), Ni (1140) and Co (336) in the lower bedded chert, Mo (438), As (149), Tl (29) and U (12) in the black shales, V (210) and Cr (87) in the massive chert, and MnO and W (24) in the manganese ore. The aluminum‐normalized profiles reveal a distinct zonation of redox‐sensitive elements: Pb‐Zn, Ni‐Co‐Cu(‐Zn) and U‐Cr in the lower bedded chert, Mo‐As‐Tl in the black shale, V(‐Cr) in the massive chert, and Mn‐Fe‐Ba‐W in the manganese ore, in ascending order. The lower and upper bedded cherts and manganese ore generally exhibit flat rare earth element patterns with positive Ce anomalies, whereas the uppermost part of the lower bedded chert, the black shale and massive chert have flat patterns with weak or nonexistent negative Ce anomalies and weak positive Eu anomalies. The strong enrichment in Ni, Co, W, Tl and As detected in the Katsuyama section is not recognized in other sediments, including those of anoxic deposition origin, but is identified in modern ferromanganese nodules, suggesting that metal enrichment in the Katsuyama section is essentially due to the formation of ferromanganese nodules rather than to deposition in an anoxic environment. The observed elemental zonation is well explained by equilibrium calculations, reflecting early diagenetic formation and associated gradual reduction with depth. The concentration profiles in combination with litho‐ and biostratigraphical features suggest that formation of these bedded manganese deposits was triggered by an influx of warm, saline and oxic water into a stagnant deep ocean floor basin in Panthalassa at the end of the middle Early Jurassic. Paleoceanographic environmental controls thus appear to be important factors in the formation and preservation of this type of stratiform manganese deposit.     

Seasonal variations in the nitrogen isotopic composition of settling particles at station K2 in the western subarctic North Pacific

Intensive observations using hydrographical cruises and moored sediment trap deployments during 2010 and 2012 at station K2 in the North Pacific Western Subarctic Gyre (WSG) revealed seasonal changes in δ ¹⁵N of both suspended and settling particles. Suspended particles (SUS) were collected from depths between the surface and 200 m; settling particles by drifting sediment traps (DST; 100–200 m) and moored sediment traps (MST; 200 and 500 m). All particles showed higher δ ¹⁵N values in winter and lower in summer, contrary to the expected by isotopic fractionation during phytoplankton nitrate consumption. We suggest that these observed isotopic patterns are due to ammonium consumption via light-controlled nitrification, which could induce variations in δ ¹⁵N(SUS) of 0.4–3.1 ‰ in the euphotic zone (EZ). The δ ¹⁵N(SUS) signature was reflected by δ ¹⁵N(DST) despite modifications during biogenic transformation from suspended particles in the EZ. δ ¹⁵N enrichment (average: 3.6 ‰) and the increase in C:N ratio (by 1.6) in settling particles suggests year-round contributions of metabolites from herbivorous zooplankton as well as TEPs produced by diatoms. Accordingly, seasonal δ ¹⁵N(DST) variations of 2.4–7.0 ‰ showed a significant correlation with primary productivity (PP) at K2. By applying the observed δ ¹⁵N(DST) vs. PP regression to δ ¹⁵N(MST) of 1.9–8.0 ‰, we constructed the first annual time-series of PP changes in the WSG. This new approach to estimate productivity can be a powerful tool for further understanding of the biological pump in the WSG, even though its validity needs to be examined carefully.     

Numerical and experimental models on the formation mechanism of collapse basins during the Green Tuff orogenesis of Japan

The geological model about volcanism of the Green Tuff geosyncline deduced from the field observations consists of the following processes:

1. Dome-shaped uplift with a mean diameter of 30 km.
2. Collapse of the central part of the domes forming basins with a mean diameter of 10 km.
3. Volcanic activity inside the collapse basins. It is considered that these consecutive processes resulted from the magmatic uplift from a deep part of the crust.

In finite element analyses performed as plane strain problems, earth's crust is assumed to be an elasto-plastic homogeneous layer and to undergo sinusoidal vertical displacement at the base of the layer due to an ascending magma reservoir. These analyses reveal that the diameter of the dome is proportional to the depth of the magma reservoir rather than to its size. The magma reservoir is estimated at 12 ～ 24 km in depth. Scale model experiments using powdered material were performed in order to reproduce a collapse basin. These three-dimensional models are reduced to a scale of 1:200,000 th of the natural size. The results of experiments show that radial and concentric cracks are produced on top of the dome and a central part encircled by concentric cracks collapses to form a basin. The boundary of the collapsed portion forms a steep cliff with a height of about 2 mm. This is equivalent to 400 m in natural size and is nearly similar to field observations.     

Development of radiation-damage halos in low-quartz: cathodoluminescence measurement after He+ ion implantation

Summary ?In cathodoluminescence (CL) images of synthetic low-quartz samples after He⁺ implantation at 4 MeV with a dose density over 1.14 × 10⁻⁴ C cm⁻², bright CL halos of about 14 μm in width from the implantation surface are recognized. These widths are consistent with the theoretical range. This confirms experimentally that the CL halos in low-quartz found in geological samples are formed by alpha radiation. It also shows that CL colour continuously changes with dose density, demonstrating that it is possible to use the CL halo as a new dosimeter that is useful for dating and analysis of radionuclide migration in natural geological media. Received December 3, 2001; revised version accepted February 27, 2002     

Chemistry and Occurrences of Native Tellurium from Epithermal Gold Deposits in Japan

The chemistry and mode of occurrences of native tellurium in the epithermal gold ores from Teine, Kobetsuzawa, Mutsu, Kawazu, Suzaki and Iriki in Japan are examined. Mineral assemblages in contact with native tellurium are: quartz‐sylvanite at Teine, quartz‐hessite‐sylvanite‐tellurantimony at Kobetsuzawa, quartz at Mutsu, quartz‐stutzite‐hessite‐sylvanite‐tetradymite at Kawazu, quartz at Suzaki, and quartz‐goldfieldite at Iriki. The peak patterns of XRD for native tellurium from these six ores are nearly identical to that of JCPDS 4–554. Their chemical compositions of Te range from 98.16 to 100.73 wt.%, showing nearly pure tellurium. Other elements detected are: Se of 0–0.85 and Cu of 0–0.74 at Teine, Sb of 0.45–0.47 and Se of 0.19–0.27 at Kawazu, Se of 0.22–1.11 and Sb of 0–0.49 at Suzaki, and Cu of 0.69–0.98, As of 0.22–0.28 and Bi of 0–0.22 wt.% at Iriki. No other elements are detected in the ores of Kobetsuzawa and Mutsu. The ranges of associated minor compositions are consistent with those of the experimental phase. The differences would be related to associate minerals. The mineral assemblages in these ores agree well with the previously proposed experimental phase relations in Au‐Ag‐Te ternary system for 120–280°C. The Suzaki ore has high Te‐Au assemblage: from calaverite‐sylvanite‐krennerite via native tellurium to petzite, with changing mineralization stage, whereas the Kobetsuzawa and the Kawazu ores have high Te‐Ag assemblage of tellurium‐hessite, and native tellurium‐stutzite‐hessite‐sylvanite, respectively. The Teine ore has intermediate assemblage of native tellurium‐sylvanite. The mineral assemblages in the Au‐Ag‐Te system are related to the hydrothermal environment especially to the pH condition, i.e. Au rich assemblages under acidic and Ag rich assemblages under intermediate pH conditions, being supported by alteration mineral species. The other telluriferous epithermal gold deposits not in association with native tellurium such as Agawa, Date, Takeno, Chugu, Chitose, Sado and Kushikino are estimated to have been formed under higher pH conditions as adularia and calcite occur in these deposits. The pH‐Eh diagram for aqueous tellurium species and tellurium minerals at 250°C indicates that the region of native tellurium occurs between those of aqueous telluride and tellurous species at lower pH, being consistent with their mineral assemblages in ores and alteration envelopes.