New compositional and optical data for antimonian and bismuthian varieties of hemusite from Japan

Summary New compositional and optical data are reported for antimonian and antimonianbismuthian varieties of hemusite from epithermal Au-Ag-Cu deposits in Japan. The empirical formula for the antimonian variety, from the Iriki mine is: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00(S_7.85Se_0.15)_8.00, and that of the Sb-Bi variety from the Kawazu mine is: (Cu_5.84Fe_0.14Ag_0.01)_5.99Mo_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07(S_7.80Se_0.12)_7.92. The theoretical formula of hemusite is Cu⁺ ₄Cu²⁺ ₂MO⁴⁺Sn⁴⁺S₈, whilst the most probable formula of the Iriki hemusite is Cu⁺ _4.5CU²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, with Sb⁵⁺ substituting for Sn⁴⁺ and forming (SbS₄)^3– tetrahedra as might be expected, given that the metal to sulphur ratio is 1, and given the sphalerite-like structure of the mineral. However Bi³⁺ cannot be so accommodated, resulting in a deficiency in (S + Se) for Kawazu hemusite. Reflectance spectra for both are compared with those of the tungsten analogue (compositional) of hemusite, kiddcreekite. The relationship between hemusitesensu stricto and these newly reported varieties is discussed in terms of simple and coupled chemical substitutions, and inferences are drawn on the valency of Sb, Bi, Mo and Cu in the hemusite structure.

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Neue chemische und optische Daten für antimon- und bismuthführende Varietäten von Hemusit aus Japan

Zusammenfassung Neue chemische und optische Daten für antimon- und bismuthführende Hemusite auf epithermalen Au-Ag-Cu Lagerstätten in Japan werden vorgelegt. Die empirische Formel für die antimon-führende Varietät aus der Iriki-Mine ist: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00 (S_7.85Se_0.15)_8.00, und die der Sb-Bi Varietät aus der Kawazu Mine ist: (Cu_5.84Fe_0.14Ag_0.01)_5.99M0_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07 (S_7.80Se_0.12)_7.92. Die theoretische Formel von Hemusit ist Cu⁺ ₄Cu²⁺ ₂Mo⁴⁺Sn⁴⁺S₈, während die wahrscheinlichere Formel für den Hemusit von Iriki Cu⁺ ₄Cu²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, mit Sb⁵⁺ an der Stelle von Sn⁴⁺, das(SbS₄)^3– Tetraeder bildet, wie zu erwarten ist, unter der Voraussetzung, da das Metall zu Schwefelverhältnis 1 und die Struktur sphaleritähnlich ist. Bi³⁺ kann jedoch nicht in dieser Weise untergebracht werden, und das führt zu einem Mangel an (S + Se) für den Hemusit von Kawazu. Die Reflektions-Spektren beider Minerale werden mit denen des Wolfram-Equivalents von Hemusit (Kiddcreekit) verglichen. Die Beziehung zwischen Hemusitsensu stricto und diesen jetzt beschriebenen Varietäten wird auf der Basis einfacher und gekoppelter chemischer Substitution diskutiert. Auf dieser Basis werden Schlüsse auf die Valenz von Sb, Bi Mo und Cu in der Hemusit-Struktur gezogen.

     

An experimental study of the grain-scale processes of peridotite melting: implications for major and trace element distribution during equilibrium and disequilibrium melting

The grain-scale processes of peridotite melting were examined at 1,340°C and 1.5 GPa using reaction couples formed by juxtaposing pre-synthesized clinopyroxenite against pre-synthesized orthopyroxenite or harzburgite in graphite and platinum-lined molybdenum capsules. Reaction between the clinopyroxene and orthopyroxene-rich aggregates produces a melt-enriched, orthopyroxene-free, olivine + clinopyroxene reactive boundary layer. Major and trace element abundance in clinopyroxene vary systematically across the reactive boundary layer with compositional trends similar to the published clinopyroxene core-to-rim compositional variations in the bulk lherzolite partial melting studies conducted at similar P–T conditions. The growth of the reactive boundary layer takes place at the expense of the orthopyroxenite or harzburgite and is consistent with grain-scale processes that involve dissolution, precipitation, reprecipitation, and diffusive exchange between the interstitial melt and surrounding crystals. An important consequence of dissolution–reprecipitation during crystal-melt interaction is the dramatic decrease in diffusive reequilibration time between coexisting minerals and melt. This effect is especially important for high charged, slow diffusing cations during peridotite melting and melt-rock reaction. Apparent clinopyroxene-melt partition coefficients for REE, Sr, Y, Ti, and Zr, measured from reprecipitated clinopyroxene and coexisting melt in the reactive boundary layer, approach their equilibrium values reported in the literature. Disequilibrium melting models based on volume diffusion in solid limited mechanism are likely to significantly underestimate the rates at which major and trace elements in residual minerals reequilibrate with their surrounding melt. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

High-sensitive measurement of uranium LIII-edge X-ray absorption near-edge structure (XANES) for the determination of the oxidation states of uranium in crustal materials

The uranium L_III-edge XANES spectra for natural rocks at the concentration range of 0.96–124 mg kg⁻¹ were measured using a log spiral bent crystal Laue analyzer (BCLA) combined with a multi-element Ge detector. It was found that the quality of the XANES spectra using the BCLA was greatly improved due to a reduction of interfering fluorescence from major components such as Rb and Sr. The ratio of signal to background intensities in the U L_III-edge XANES spectra increased by a factor of 2.9–17 with the use of the BCLA, which greatly enhanced the detection limit for the speciation of the oxidation states of U or the U(IV)/U(VI) ratio of natural samples. In addition, it was demonstrated that the fluorescence XANES method coupled with the BCLA enable determination of the speciation of U for various natural samples such as acidic igneous rocks, ferromanganese nodules, sediments, and some sedimentary rocks such as shale and limestone.     

Crystal chemical significance of chemical zoning in dissakisite-(Ce)

Dissakisites from Trimouns dolomite mine, France, have two kinds of single crystals: chemical-zoned and homogeneous types. Back-scattered electron microprobe (BSE) images of these dissakisites reveal both Ca–Al rich dark zones and Fe-ΣREE rich bright zones. Crystal structures of three dark and two bright zones in a chemical-zoned dissakisite and of a homogeneous zone in unzoned dissakisite were refined to individual R indices (about 3.0–5.0%) based on 1,400 observed [|F ₀| > 4σF ₀] reflections measured with MoKα X-radiation using the single crystal diffractometer. The differences in brightness between their BSE images arise from those in coupled substitutions of the elements occupying A2 and M3 sites. The main reason for these differences is that ten-coordinated A2 polyhedra and M3 octahedra are directly linked through their shared edge, which creates a great potential for making this coupled substitution. This zoning indicates that formation of the whole zoned crystal, where each zone could be grown steadily with its crystallographic axes mutually parallel to each other, may be identified as autoepitaxy.     

Contamination of organotin compounds and imposex in molluscs from Vancouver,Canada

Gastropods and bivalves were collected at 15 sites at Vancouver and Victoria, Canada between 24 May and 7 June, 1999, to establish tissue concentrations of butyltin and phenyltin compounds, to record imposex symptoms in gastropods, and to assess the present status of organotin contamination around Vancouver. No neogastropods (such as Nucella lima) were found around Vancouver. Neogastropod populations could have been extirpated by severe TBT contamination in Vancouver, as relatively high concentrations of TBT were detected in tissues of Mytilus trossulus from Vancouver, and the neogastropods distributed in Vancouver might be sensitive to TBT. Recovery from imposex, however, was observed in neogastropod populations from three sites at Victoria and Mission Point. TBT contamination has continued around Vancouver, arising from continuous use of TBT in antifouling paints for vessels larger than 25 m in length; however, TBT has decreased around Victoria and Mission Point. Different patterns of TBT accumulation in tissue were observed among the bivalve species from Vancouver. The highest TBT concentration detected in Tresus capax suggested some possible adverse effects. TBT was the most predominant butyltin component in almost all bivalve specimens surveyed, suggesting a low rate of TBT metabolism. Phenyltin compounds were not detected in any molluscan specimens in this study.     

Nitrogen budget in Tokyo Bay with special reference to the low sedimentation to supply ratio

In order to determine why the sedimentation to supply ratio of nutrients in Tokyo Bay is markedly small, the nitrogen budget was investigated for 1979, when a systematic and continuous observation of flow and salinity was carried out. The data were analyzed by use of a simple advective-diffusive box model and dissolved oxygen balance in the lower layer was also examined. The calculated values of two-layer flow, settling, primary production, mineralization, denitrification, and dissolved oxygen consumption were comparable to those observed.The factors making the sedimentation to supply ratio makedly small were summarized as: 1) a strong and stable two-layer flow generated by a large freshwater supply, 2) further intensification of this two-layer flow by the northern winter monsoon, 3) coincidence of the discharge region with the supply region of nutrients caused by the transverse inclination of the interface, probably due to the earth's rotation. 4) effective discharge of nutrients from the bay due to a strong tidal flow and a possible cyclonic tidal residual circulation in the inner bay mouth, 5) incomplete consumption of nutrient salts by phytoplankton in the upper layer even in the most productive season, and 6) possible denitrification in the anaerobic bottom water in summer and in the bottom sediment itself throughout the year in the inner bay.     

Annual Anthropogenic Carbon Transport into the North Pacific Intermediate Water through the Kuroshio/Oyashio Interfrontal Zone: An Estimation from CFCs Distribution

Vertical distribution of anthropogenic carbon content of the water (exDIC) in the Oyashio area just outside of the Kuroshio/Oyashio Interfrontal Zone (K/O Zone) was estimated by the simple 1-D advection-diffusion model calibrated by the distribution of chlorofluorocarbons (CFCs). The average concentration of exDIC for = 26.60–27.00 is multiplied by the volume transport of Oyashio water into the North Pacific Intermediate Water (NPIW) to estimate the annual transport of exDIC into NPIW through K/O Zone. The estimated transport of exDIC was 0.018–0.020 GtC/y, which corresponds to 15% of the whole total exDIC accumulation in the temperate North Pacific. A simple assessment using the NPIW 1-box model indicates that the current study explains at least 70% of the total annual transport of exDIC into NPIW, and that small exDIC sources for NPIW still exists in addition to K/O Zone.     

Effects of salinity downshock on dimethylsulfide production

During time-series observations in Sagami Bay, Japan, the concentration of dissolved dimethylsulfoniopropionate (DMSP_d), a precursor of dimethylsulfide (DMS), was negatively correlated with salinity. In the laboratory, low-salinity shock reduced DMS production rates of the natural bacterial community and induced rapid DMSP release from a dinophyte, Heterocapsa triquetra, suggesting that low-salinity shock reduced DMSP_d consumption but enhanced DMSP_d production, which agrees with the negative correlation between DMSP_d and salinity observed in Sagami bay. In addition, low-salinity shock did not affect DMSP lyase activity of H. triquetra. Low-salinity shock would increase the contribution from algae in DMS production, leading to an increase in potential DMS productivity in the environment.     

Structure of Subsurface Intrusion of the Oyashio Water into the Kuroshio Extension and Formation Process of the North Pacific Intermediate Water

In order to understand the actual formation process of the North Pacific Intermediate Water (NPIW), structure of subsurface intrusions of the Oyashio water and the mixing of the Oyashio and the Kuroshio waters in and around the Kuroshio Extension (KE) were examined on the basis of a synoptic CTD observation carried out in May-June 1992. The fresh Oyashio water in the south of Hokkaido was transported into KE region through the Mixed Water Region (MWR) in the form of subsurface intrusions along two main paths. The one was along the east coast of northern Japan through the First Branch of the Oyashio (FBO) and the other along the eastern face of a warm streamer which connected KE with a warm core ring through the Second Branch of the Oyashio (SBO). The fresh Oyashio water extended southward through FBO strongly mixed with the saline NPIW transported by the Kuroshio in the south of Japan (old NPIW) in and around the warm streamer. On the other hand, the one through SBO well preserved its original properties and extended eastward beyond 150°E along KE with a form of rather narrow band. The intrusion ejected Oyashio water lens with a diameter of 50–60 km southward across KE axis and split northward into the MWR involved in the interaction of KE and a warm core ring, which were supposed to be primary processes of new NPIW formation.     

Ce and Nd isotope geochemistry on island arc volcanic rocks with negative Ce anomaly: existence of sources with concave REE patterns in the mantle beneath the Solomon and Bonin island arcs

¹³⁸Ce/¹⁴²Ce isotope ratios in Cenozoic island arc volcanic rocks are reported for the first time, together with isotope ratios of Nd and Sr and abundances of REE, Ba and Sr. The island arc volcanics studies here are boninites from Chichijima, the Bonin Islands, and basalts and andesites from the Solomon Islands. REE patterns of the island arc volcanic rocks from the Solmon Islands and the Bonin Islands are confirmed to have negative Ce anomalies. It is also disclosed that the majority of these island arc volcanic rocks show mainly positive values for both _Ce and _Nd. It is shown that these _Ce and _Ce values can hardly be interpreted by simple mixing between MORB and oceanic or continental crustal rocks; the former have positive _Nd and negative _Ce and the latter have negative _Ce and positive or negative _Nd. Existence of sources having positive _Ce and _Nd values is strongly suggested. If the sources are assumed to have been fractionated from CHUR (chondritic uniform reservoir) at the early or middle Precambrian era, the sources from which the volcanics were derived are concluded to have kept concave REE patterns with larger (La/Ce)_N and smaller (Nd/Sm)_N ratios than chondritic values over a substantial period of time, until the time of Cenozoic magmatism forming island arc volcanic rocks in question. During the periods of the Cenozoic magmatic activities and their related events, Ce anomalies are considered to have been created. From Ce and Nd isotope ratios, however, it is difficult to determine which of the following processes was responsible for the Ce anomaly; the incorporation process of subducted oceanic crust into magma at the mantle or the slab dehydration and metasomatism process. Nevertheless, so far as Ce and Nd isotopic ratios are concerned, incorporation of oceanic sediments did not take place to any clearly detectable degree.