Seasonal variation of volatile organic iodine compounds in the water column of Funka Bay,Hokkaido, Japan

Volatile organic iodine compounds (VOIs) emitted from the ocean surface to the air play an important role in atmospheric chemistry. Shipboard observations were conducted in Funka Bay, Hokkaido, Japan, bimonthly or monthly from March 2012 to December 2014, to elucidate the seasonal variations of VOI concentrations in seawater and their sea-to-air iodine fluxes. The bay water exchanges with the open ocean water of the North Pacific twice a year (early spring and autumn). Vertical profiles of CH₂I₂, CH₂ClI, CH₃I, and C₂H₅I concentrations in the bay water were measured bimonthly or monthly within an identified water mass. The VOI concentrations began to increase after early April at the end of the diatom spring bloom, and represented substantial peaks in June or July. The temporal variation of the C₂H₅I profile, which showed a distinct peak in the bottom layer from April to July, was similar to the PO₄ ^3? variation profile. Correlation between C₂H₅I and PO₄ ^3? concentrations (r = 0.93) suggests that C₂H₅I production was associated with degradation of organic matter deposited on the bottom after the spring bloom. CH₂I₂ and CH₂ClI concentrations increased substantially in the surface and subsurface layers (0–60 m) in June or July resulted in a clear seasonal variation of the sea-to-air iodine flux of the VOIs (high in summer or autumn and low in spring).     

Strong interaction between the ring system and the ionosphere of saturn

An abnormally low electron density in the Saturnian ionosphere observed by the radio occultation experiment of the Pioneer 11 may be explained in terms of the contamination of water in the Saturnian upper atmosphere from its ring system.     

Nd and Sr isotopic variations in acidic rocks formed under a peculiar tectonic environment in Miocene Southwest Japan

Initial Nd and Sr isotopic ratios were obtained for middle Miocene igneous rocks as well as for related rocks from the Outer Zone of Southwest Japan to investigate the petrogenesis of acidic magmas and their relation to a peculiar tectonic environment bearing on the back-arc spreading of the Japan Sea. On the _Nd- _Sr diagram, data points for the acidic rocks fall in the – _Nd, + _Sr quadrant occupying different positions from those for sedimentary and old crustal rocks, and seem to define several subparallel lines which extend towards the lower-righthand sedimentary field. The S-type acidic rocks occupy an intermediate position between I-type rocks and sedimentary ones, a fact suggesting mixing of an igneous component and a sedimentary one. The linear mixing trend observed on the _Nd- _Sr diagram can be attained in the restricted case that the igneous component has similar Sr/Nd concentration ratios to that of the sedimentary one, which implies an intermediate to acidic composition for the igneous component. Inconsistency between the elemental and isotopic variations observed may be reconciled by considering that mixing, probably in the relatively deep part of the crust, might have occured prior to chemical differentiation processes. The episodic igneous activity and the high heat energy required to melt such materials involving sedimentary rocks may be explained by a model in which a hot mantle region probably corresponding to the rising part of the mantle convection supplied the heating energy to the Outer Zone of Southwest Japan when passing beneath Southwest Japan in the course of movement of the hot rising part from the Shikoku basin areas to the Japan Sea area.     

Spatial distribution of deuterium in atmospheric water vapor: Diagnosing sources and the mixing of atmospheric moisture

We measured the stable isotopic composition of hydrogen (δD) within atmospheric water vapor collected simultaneously at six sites in the vicinity of a lake (Lake Kasumigaura, Eastern Japan) to determine its spatial distribution characteristics and thereby diagnose sources and mixing of atmospheric moisture. The measured spatial distribution of δD showed no relation to distance from the lake, although it showed a correlation with the distribution of the water-vapor mixing ratio Q. For two of the three sampling days, we found a simple two-component (i.e., water vapor transpiring from local land surfaces and pre-existing vapor in the background atmosphere) mixing line in a Keeling plot (i.e., δ − 1/Q diagram). On a third day, however, contributions from lake evaporation were detected in addition to the above components. On this day, lake-derived vapor accounted for approximately 10-20% of atmospheric water vapor at the sites located leeward of the lake. The observed differences in mixing patterns among sampling days can be explained by a simple atmospheric moisture budget. Thus, it is likely that simultaneous isotopic measurements of atmospheric water vapor at multiple locations with aid of Keeling plot are capable of giving us useful information in diagnosing the sources and mixing pattern of the vapor.     

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.

     

Reaction-induced grain boundary cracking and anisotropic fluid flow during prograde devolatilization reactions within subduction zones

Devolatilization reactions during prograde metamorphism are a key control on the fluid distribution within subduction zones. Garnets in Mn-rich quartz schist within the Sanbagawa metamorphic belt of Japan are characterized by skeletal structures containing abundant quartz inclusions. Each quartz inclusion was angular-shaped, and showed random crystallographic orientations, suggesting that these quartz inclusions were trapped via grain boundary cracking during garnet growth. Such skeletal garnet within the quartz schist formed related to decarbonation reactions with a positive total volume change (?V _t > 0), whereas the euhedral garnet within the pelitic schists formed as a result of dehydration reaction with negative ?V _t values. Coupled hydrological–chemical–mechanical processes during metamorphic devolatilization reactions were investigated by a distinct element method (DEM) numerical simulation on a foliated rock that contained reactive minerals and non-reactive matrix minerals. Negative ?V _t reactions cause a decrease in fluid pressure and do not produce fractures within the matrix. In contrast, a fluid pressure increase by positive ?V _t reactions results in hydrofracturing of the matrix. This fracturing preferentially occurs along grain boundaries and causes episodic fluid pulses associated with the development of the fracture network. The precipitation of garnet within grain boundary fractures could explain the formation of the skeletal garnet. Our DEM model also suggests a strong influence of reaction-induced fracturing on anisotropic fluid flow, meaning that dominant fluid flow directions could easily change in response to changes in stress configuration and the magnitude of differential stress during prograde metamorphism within a subduction zone.     

Near-infrared and Visible Light Microthermometry of Fluid Inclusions in Sphalerite from a Possible Southeast Extension of the Toyoha Polymetallic Deposit, Japan

Abstract. Near-infrared (NIR) and visible light microthermometry was applied to the fluid inclusions in sphalerite from a possible southeast extension of the Toyoha polymetallic deposit. Sphalerite occurs as euhedral-subhedral crystals or collo-form aggregates with a variety of color, which contain a well-developed growth banding. Combined with morphological observations, fluid inclusions in dark-colored sphalerite were examined using a near-infrared light microscopic technique, whereas those in light-colored sphalerite and quartz were examined by a conventional visible light microscopy.
Salinities of fluid inclusions in dark-colored sphalerite have a wide variation (1.0–10.3 wt % NaCl equiv.) compared to that in light-colored sphalerite and quartz (0.0–3.4 wt % NaCl equiv.). These variations suggest that the conventional microthermometric data from light-colored sphalerite and quartz were inadequate to interpret the ore formation process. Dark-colored colloform sphalerite and a dark core of subhedral sphalerite formed from high-salinity fluids (6.5–10.3 wt % NaCl equiv.) under highly supersaturated conditions with respect to sphalerite.
The NIR and visible light microthermometry of fluid inclusions in sphalerite combined with its morphological observations is an invaluable method to infer the formation conditions of sphalerite. The NIR and visible light microthermometry is useful to reveal how the nature of ore fluids changed with time.     

Disturbance of recruitment success of mantis shrimp in Tokyo Bay associated with effects of hypoxia on the early life history

We investigated effects of severe hypoxia (dissolved oxygen <1 ml l⁻¹) on recruitment of mantis shrimp Oratosquilla oratoria in Tokyo Bay. Ten-year field surveys were conducted to examine quantitative relationships in annual mean densities of larvae and juveniles, and spatial distribution of juveniles and severe hypoxia. There was no significant correlation between annual mean densities of larvae and juveniles, suggesting that mortality during larval or juvenile stages varies among years, which might have regulated abundance of young-of-the-year juveniles. Juvenile density was low in the severely hypoxic area, implying that hypoxia could affect survivals and spatial distribution of juveniles. Meanwhile, there are yearly fluctuations in juvenile density in normoxic areas of both northern and southern part of the bay. This evidence suggests that abundance of post-settled juveniles might have been determined by not only effects of hypoxia, but also other factors influencing mortality during the early life stages.     

Iron and zinc partitioning between coexisting stannite and sphalerite: a possible indicator of temperature and sulfur fugacity

Stannite and sphalerite coexisting with iron sulfides (pyrite and/or pyrrhotite) from Japanese ore deposits associated with tin mineralization were analyzed. Based on the iron and zinc partitioning between stannite and sphalerite, the formation temperature and sulfur fugacity for this mineral assemblage were estimated. A good correlation between stannite-sphalerite temperatures and filling temperatures of fluid inclusions and sulfur isotope temperatures was obtained. This good correlation suggests that the stannite-sphalerite pair is a useful indicator of temperature and sulfur fugacity. It is deduced that the formation temperatures are not different for skarn-type, polymetallic vein-type and Sn-W vein-type deposits, whereas the sulfur fugacities are different; sulfur fugacities increase from the skarn-type through the Sn-W vein-type to the polymetallic vein-type deposits.