Mineralogical alteration of a type A CAI from Allende CV3 chondrite: Formation of secondary dmisteinbergite and its phase transition to anorthite

Dmisteinbergite, a hexagonal form of CaAl₂Si₂O₈, was found in a compact type A Ca-Al-rich inclusion (CAI) in the Allende CV3 chondrite. Scanning and transmission electron microscopic observations show that dmisteinbergite was always in contact with grossular and grossular was in contact with melilite. In addition, there is a crystallographic relationship between dmisteinbergite and anorthite. Based on the textural and crystallographic evidence, the following mineralogical alteration processes are proposed to have occurred in the CAI. (1) Melilite was replaced by grossular. High densities of vesicles in the grossular indicate that hydrogrossular might have been the primary alteration phase and dehydrated by later metamorphism. (2) Dmisteinbergite formed from (hydro)grossular through a reaction with Si-rich fluid. (3) Nano-sized minerals are formed within dmisteinbergite. (4) Dmisteinbergite was transformed to anorthite. (5) Both anorthite and dmisteinbergite were altered to nepheline. (6) Hydrogrossular was dehydrated to grossular. (Hydro)grossular, dmisteinbergite, anorthite, and nepheline in the CAI seem to have formed in the course of metasomatism that occurred in the Allende parent body. Except for the hydrogrossular dehydration, these reactions could have occurred at moderate temperature (200–250°C) in high pH fluids (pH 13–14) according to past experimental studies. Episodic changes in fluid composition seem to have occurred before reactions (2), (4), and (5), because these reactions were not completed before the next reaction started. Higher temperature is required for reactions (5) and (6) to occur. Our observation of the CAI suggests that it experienced multiple episodes of metasomatism as temperatures were rising in the Allende parent asteroid.     

Phase separation,fluid mixing,and origin of the greisens and potassic episyenite associated with the Água Boa pluton,Pitinga tin province,Amazonian Craton,Brazil

Based on petrographical data, three types of greisen have been characterized at the western border of Água Boa pluton: siderophyllite–topaz–quartz greisen (greisen 1), fluorite–phengite–quartz greisen (greisen 2) and quartz–chlorite–phengite greisen (greisen 3). Episyenites were also identified.Two fluids of independent origin interacted with the same protolith – a hornblende-biotite alkali feldspar granite – and produced both the greisens and potassic episyenite: (1) an acid, low-salinity (4–12 wt.% NaCl eq.), F-rich, relatively hot (400–350 °C) reduced aqueous-carbonic fluid (CH₄–H₂O–NaCl–FeCl₂ ± KCl), which by immiscibility gave rise to fluid IA (aqueous) and IC (carbonic); and (2) a lower salinity (2–4 wt.% NaCl eq.) and temperature (200–150 °C) aqueous fluid (H₂O–NaCl), which was responsible for all dilution processes. Fluid 1 seems to have had a magmatic-hydrothermal origin, while fluid 2 is probably surface-derived (meteoric water?). An alkaline, F-poorer and diluted equivalent of fluid IA was interpreted to have caused the episyenitization of the granite host rock as well as the formation of phengite-rich greisen 3. The continuos interaction of this fluid with the potassic episyenite produced a moderate- to high-salinity (20–24 wt.% NaCl eq.), low-temperature (200–100 °C) fluid (H₂O–NaCl–CaCl₂ ± KCl), leading to the formation of chlorite-rich zone of greisen 3 and late silicification of potassic episyenite.In the greisen 1, decreasing F-activity and increasing oxygen fugacity, as the system cooled down, favored the formation of a topaz-rich inner zone, which grades into a siderophyllite-rich zone outwardly. Greisen 2 was formed under more oxidizing conditions by fluids poorer in F than those trapped in the siderophyllite-rich zone.The oxidation of aqueous-carbonic fluid took place at three distinct stages: (i) below the FMQ buffer; (ii) between the FMQ and NNO buffers; and (iii) above the NNO buffer.The dissolution cavities generated during the episyenitization process increased the permeability of the altered rocks, resulting in an increase of the fluid/rock ratios at the potassic episyenite and greisen 3 sites.All these fluids were trapped under pressure conditions of <1.0 kbar, representing shallow crustal levels and are consistent with those that have been estimated for the Pitinga tin–granites.The oxygen fugacity, F-activity gradients and salinity variations that occurred during the cooling of the hydrothermal system, in addition to differences in permeability, were important factors in the formation of distinct greisens. They not only controlled the fluid compositional changes, but also caused the cassiterite and sulfide precipitation at the greisen sites.     

The Cretaceous Ofuku Pluton and Its Relation to Mineralization in the Western Akiyoshi Plateau,Yamaguchi Prefecture,Japan

The relationship between the magmatism of the Cretaceous Ofuku pluton and mineralization in and around the Akiyoshi Plateau, Yamaguchi Prefecture, Japan was investigated using a combination of field observation, petrographic and geochemical analyses, K–Ar geochronology, and fluid inclusion data. The Ofuku pluton has a surface area of 1.5 × 1.0 km, and was intruded into the Paleozoic accretionary complexes of the Akiyoshi Limestone, Ota Group and Tsunemori Formation in the western part of the Akiyoshi Plateau. The pluton belongs to the ilmenite‐series and is zoned, consisting mainly of early tonalite and granodiorite that share a gradational contact, and later granite and aplite that intruded the tonalite and granodiorite. Harker diagrams show that the Ofuku pluton has intermediate to silicic compositions ranging from 60.4 to 77.9 wt.% SiO₂, but a compositional gap exists between 70.5 to 73.4 wt.% SiO₂ (anhydrous basis). Modal and chemical variations indicate that the assumed parental magma is tonalitic. Quantitative models of fractional crystallization based on mass balance calculations and the Rayleigh fractionation model using major and trace element data for all crystalline phases indicate that magmatic fractionation was controlled mainly by crystal fractionation of plagioclase, hornblende, clinopyroxene and orthopyroxene at the early stage, and quartz, plagioclase, biotite, hornblende, apatite, ilmenite and zircon at the later stage. The residual melt extracted from the granodiorite mush was subsequently intruded into the northern and western parts of the Ofuku pluton as melt lens to form the granite and aplite. The age of the pluton was estimated at 99–97 Ma and 101–98 Ma based on K–Ar dating of hornblende and biotite, respectively. Both ages are consistent within analytical error, indicating that the Ofuku pluton and the associated Yamato mine belong to the Tungsten Province of the San‐yo Belt, which is genetically related to the ilmenite‐series granitoids of the Kanmon to Shunan stages. The aplite contains Cl‐rich apatite and REE‐rich monazite‐(Ce), allanite‐(Ce), xenotime and bastnäsite‐(Ce), indicating that the residual melt was rich in halogens and REEs. The tonalite–granodiorite of the Ofuku pluton contains many three‐phase fluid inclusions, along with daughter minerals such as NaCl and KCl, and vapor/liquid (V/L) volume ratios range from 0.2 to 0.9, suggesting that the fluid was boiling. In contrast, the granite and aplite contain low salinity two‐phase inclusions with low V/L ratios. The granodiorite occupies a large part of the pluton, and the inclusions with various V/L ratios with chloride daughter minerals suggest the boiling fluids might be related to the mineralization. This fluid could have carried base metals such as Cu and Zn, forming Cu ore deposits in and around the Ofuku pluton. The occurrence and composition of fluid inclusions in the igneous rocks from the Akiyoshi Plateau are directly linked to Cu mineralization in the area, demonstrating that fluid inclusions are useful indicators of mineralization.     

Characteristics of the ratio of dissolved cadmium to phosphate in subtropical coastal waters of Ishigaki Island,Okinawa, Japan

The ratio of dissolved cadmium (Cd) to phosphate (PO₄) in the subtropical coastal area of Ishigaki Island, Okinawa, Japan, was investigated. Twenty vertical seawater samplings were carried out once a month from May 2008 to January 2010. In order to examine how the Cd/PO₄ ratio in seawater varies with the oceanographic conditions (i.e., the water temperature–salinity characteristics), the water masses at the study sites were classified into two types: group 1 with a water temperature of >25°C and a salinity range of 34.0–34.4, and group 2 with a water temperature of <25°C and a salinity of >34.4. A different phytoplankton assemblage was observed in each water mass defined. Different Cd/PO₄ ratios were obtained for the two water mass types, due to the differences between the types in terms of the environmental conditions such as the water temperature–salinity (T–S) characteristics and phytoplankton assemblages, as well as possible variations in the concentrations of dissolved iron, zinc, manganese, and CO₂ in seawater in each water mass.     

Fluid inclusion and stable isotope (O, H, C, and S) constraints on the genesis of the Serrinha gold deposit, Gurupi Belt, northern Brazil

The Serrinha gold deposit of the Gurupi Belt, northern Brazil, belongs to the class of orogenic gold deposits. The deposit is hosted in highly strained graphitic schist belonging to a Paleoproterozoic (∼2,160 Ma) metavolcano-sedimentary sequence. The ore-zones are up to 11 m thick, parallel to the regional NW–SE schistosity, and characterized by quartz-carbonate-sulfide veinlets and minor disseminations. Textural and structural data indicate that mineralization was syn- to late-tectonic and postmetamorphic. Fluid inclusion studies identified early CO₂ (CH₄-N₂) and CO₂ (CH₄-N₂)-H₂O-NaCl inclusions that show highly variable phase ratios, CO₂ homogenization, and total homogenization temperatures both to liquid and vapor, interpreted as the product of fluid immiscibility under fluctuating pressure conditions, more or less associated with postentrapment modifications. The ore-bearing fluid typically has 18–33mol% of CO₂, up to 4mol% of N₂, and less than 2mol% of CH₄ and displays moderate to high densities with salinity around 4.5wt% NaCl equiv. Mineralization occurred around 310 to 335°C and 1.3 to 3.0 kbar, based on fluid inclusion homogenization temperatures and oxygen isotope thermometry with estimated oxygen fugacity indicating relatively reduced conditions. Stable isotope data on quartz, carbonate, and fluid inclusions suggest that veins formed from fluids with δ¹⁸O_H2O and δD_H2O (310–335°C) values of +6.2 to +8.4‰ and −19 to −80‰, respectively, which might be metamorphic and/or magmatic and/or mantle-derived. The carbon isotope composition (δ¹³C) varies from −14.2 to −15.7‰ in carbonates; it is −17.6‰ in fluid inclusion CO₂ and −23.6‰ in graphite from the host rock. The δ³⁴S values of pyrite are −2.6 to −7.9‰. The strongly to moderately negative carbon isotope composition of the carbonates and inclusion fluid CO₂ reflects variable contribution of organic carbon to an originally heavier fluid (magmatic, metamorphic, or mantle-derived) at the site of deposition and sulfur isotopes indicate some oxidation of the originally reduced fluid. The deposition of gold is interpreted to have occurred mainly in response to phase separation and fluid-rock interactions such as CO₂ removal and desulfidation reactions that provoked variations in the fluid pH and redox conditions.     

Ridge collision and in situ greenstones in accretionary complexes: An example from the Late Cretaceous Ryukyu Islands and southwest Japan margin

Abstract Mélange units containing greenstones are common throughout the Cretaceous-Miocene Shimanto Supergroup in the Ryukyu Is and southwest Japan. Most greenstones in the accretionary complex originated in oceanic spreading ridges and seamounts, and they formed far from the convergent margin. Some mélange-like units in the supergroup, however, contain greenstones that were extruded upon and intruded into unconsolidated fine-grained terrigenous clastic sediments. It is inferred that eruption of the in situ greenstones resulted from igneous activity in the trench area. Geochemical signatures indicate that the greenstone protoliths were similar to mafic lavas generated at spreading ridges. Fossil ages of the strata containing in situ greenstones become younger over a distance of 1300 km eastward from Amami-Oshima (Cenomanian-Turonian) in the Ryukyu Is to central Japan (Late Maestrichtian-earliest Paleocene), implying that a site of igneous activity in the trench area migrated eastward along the Ryukyu Is and southwest Japan margin. Plate reconstructions of the northwest Pacific Ocean suggest the presence of the Kula-Pacific ridge near Late Cretaceous to early Paleogene Japan. In this context, it is suggested that the greenstones formed in response to Kula-Pacific ridge-forearc collision.
Ancient ridge-forearc collisions are best recognized by the presence of mid-ocean ridge basalt (MORB) extruded on sediments inferred to have accumulated in the trench area. Diachronous occurrences of the strata associated with these MORB in an orogenic belt are useful for documenting the ridge collision through time.     

Generation of unsaturated and aromatic hydrocarbons by thermal alteration of young kerogen

Monounsaturated, monoaromatic and polyaromatic hydrocarbons generated by artificial thermal alteration of young marine (Tanner basin, offshore California) kerogen were studied by computerized GC-MS. Their relative amounts changed with temperature (150–410°C) and time (5–120 hr) of heating as follows: Monounsaturates → Monoaromatics → Polyaromatics. Distribution of alkyl homologs of phenanthrene also changed with increasing degree of thermal alteration. These results are in agreement with those observed for crude oils and shales.     

K-Ar dating studies of Ashigawa and Tokuwa granodiorite bodies and plutonic geochronology in the South Fossa Magna, central Japan

Abstract K-Ar age studies in the Ashigawa and the southern part of the Tokuwa granodioritic bodies, which consist of the southern part of the Kofu plutonic complex, revealed that they formed between 12 and 9 Ma. Quite a narrow range of ages obtained from the Ashigawa southernmost part of the Tokuwa pluton implies that they cooled rapidly. The southern part of the Tokuwa pluton, as a whole, shows a systematic age distribution with a decrease in age to the north. Compilation of currently available plutonic ages in the South Fossa Magna suggests that the plutonic activities occurred three times in this region. Episodic activity like this could be argued in relation to the tectonic development of this region.