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.     

Roles of Biogeochemical Processes in the Oceanic Carbon Cycle Described with a Simple Coupled Physical-Biogeochemical Model

To evaluate the contribution of biogeochemical processes to the oceanic carbon cycle and to calculate the ratio of calcium carbonate to organic carbon downward export, we have incorporated biological and alkalinity pumps in the yoked high-latitude exchange/interior diffusion-advection (YOLDA) model. The biogeochemical processes are represented by four parameters. The values of the parameters are tuned so that the model can reproduce the observed phosphate and alkalinity distributions in each oceanic region. The sensitivity of the model to the biogeochemical parameters shows that biological production rates in the euphotic zone and decomposition depths of particulate matters significantly influence horizontal and vertical distributions of biogeochemical substances. The modeled vertical fluxes of particulate organic phosphorus and calcium carbonate are converted to vertical carbon fluxes by the biological pump and the alkalinity pump, respectively. The downward carbon flux from the surface layer to the deep layer in the entire region is estimated to be 3.36 PgC/yr, which consists of 2.93 PgC/yr from the biological pump and 0.43 PgC/yr from the alkalinity pump, which is consistent with previous studies. The modeled rain ratio is higher with depth and higher in the Pacific and Indian Oceans than in the Atlantic Ocean. The global rain ratio at the surface layer is calculated to be 0.14 to 0.15. This value lies between the lower and higher ends of the previous estimates, which range widely from 0.05 to 0.25. This study indicates that the rain ratio is unlikely to be higher than 0.15, at least in the surface waters.     

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.     

Processes Causing the Temporal Changes in Si/N Ratios of Nutrient Consumptions and Export Flux during the Spring Diatom Bloom

Two processes are generally explained as causes of temporal changes in the stoichiometric silicon/nitrogen (Si/N) ratios of sinking particles and of nutrient consumption in the surface water during the spring diatom bloom: (1) physiological changes of diatom under the stress of photosynthesis of diatom and (2) differences of regeneration between silicon and nitrogen. We investigated which process plays an important role in these changes using a one-dimensional ecosystem model that explicitly represents diatom and the other non-silicious phytoplankton. The model was applied to station A7 (41°30′ N, 145°30′ E) in the western North Pacific, where diatom regularly blooms in spring. Model simulations show that the Si/N ratios of the flux exported by the sinking particles at 100 m depth and of nutrient consumptions in the upper 100 m surface water have their maxima at the end of the spring diatom bloom, the values and timings of which are significantly different from each other. Analyses of the model results show that the differences of regeneration between silicon and nitrogen mainly cause the temporal changes of the Si/N ratios. On the other hand, the physiological changes of diatoms under stress can hardly cause these temporal changes, because the effect of the change in the diatom's uptake ratio of silicon to nitrogen is cancelled by that in its sinking rate.     

An Ecosystem Model Coupled with Nitrogen-Silicon-Carbon Cycles Applied to Station A7 in the Northwestern Pacific

A model based on that of Kishi et al. (2001) has been extended to 15 compartments including silicon and carbon cycles. This model was applied to Station A7 off Hokkaido, Japan, in the Northwestern Pacific. The model successfully simulated the observations of: 1. a spring bloom of diatoms; 2. large seasonal variations of nitrate and silicate concentrations in the surface water; and 3. large inter-annual variations in chlorophyll-a. It also reproduced the observed features of the seasonal variations of carbon dioxide partial pressure (pCO₂)—a peak in pCO₂ in winter resulting from deep winter convection, a rapid decrease in pCO₂ as a result of the spring bloom, and an almost constant pCO₂ from summer through fall (when the effect of increasing temperature cancels the effect of biological production). A comparison of cases with and without silicate limitation shows that including silicate limitation in the model results in: 1. decreased production by diatoms during summer; and 2. a transition in the dominant phytoplankton species, from diatoms to other species that do not take up silicate. Both of these phenomena are observed at Station A7, and our results support the hypothesis that they are caused by silicate limitation of diatom growth. This revised version was published online in July 2006 with corrections to the Cover Date.     

A Comparison of Simulated Particle Fluxes Using NEMURO and Other Ecosystem Models in the Western North Pacific

JGOFS has revealed the importance of marine biological activity to the global carbon cycle. Ecological models are valuable tools for improving our understanding of biogeochemical cycles. Through a series of workshops, the North Pacific Marine Science Organization (PICES) developed NEMURO (North Pacific Ecosystem Model Understanding Regional Oceanography) a model, specifically designed to simulate the lower trophic ecosystem in the North Pacific Ocean. Its ability to simulate vertical fluxes generated by biological activities has not yet been validated. Here compare NEMURO with several other lower trophic level models of the northern North Pacific. The different ecosystem models are each embedded in a common three-dimensional physical model, and the simulated vertical flux of POM and the biomass of phytoplankton are compared. The models compared are: (1) NEMURO, (2) the Kishi and Nakata Model (Kishi et al., 1981), (3) KKYS (Kawamiya et al., 1995, 2000a, 2000b), and (4) the Denman model (Denman and Peña, 2002). With simple NPZD models, it is difficult to describe the production of POM (Particulate Organic Matter) and hence the simulations of vertical flux are poor. However, if the parameters are properly defined, the primary production can be well reproduced, even though none of models we used here includes iron limitation effects. On the whole, NEMURO gave a satisfactory simulation of the vertical flux of POM in the northern North Pacific.     

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.