MIS11–19 pollen stratigraphy from the 250-m Choshi core, northeast Boso Peninsula, central Japan: Implications for the early/mid-Brunhes (400–780 ka) climate signals

Abstract   The 250-m Choshi core (CHOSHI-1), drilled from hemipelagic muds of the Inubo Group, has been physically, geochemically and tephrochronologically analyzed back to 1 Ma. We provide pollen results for the 19–169 m section of the core (400–780 ka) bracketed by the marker tephra Ty1 (equivalent to J4) and the Brunhes–Matuyama paleomagnetic boundary. The results show good agreement with the corresponding oxygen isotope (δ¹⁸O) profile, with high δ¹⁸O intervals dominated by boreal conifers Picea , Abies , Pinus (subgen. Haploxylon ) and Tsuga ( diversifolia ), whereas low δ¹⁸O intervals are dominated by temperate conifers Cryptomeria , Taxaceae-Cephalotaxaceae-Cupressaceae and Sciadopitys . In order to confirm pollen-climate relations for the relevant taxa, a modern surface pollen dataset for the Japanese archipelago was consulted. In this analysis, the ratios of Cryptomeria / Picea and temperate/boreal conifers serve as proxies for the 100-kyr glacial/interglacial cycle during the Middle Pleistocene. Distinct signals for marine isotope stages (MIS) 11, 12, 13–15, 16, 17 and 18–19 are recognized in accordance with the tephrochronology and δ¹⁸O of the same core. Application of the criteria to an independent pollen record from Lake Biwa provides an integrated pollen stratigraphy for mid-latitude Japan during the past 800 ky. Some degree of uncertainty remains in the chronology of the MIS13–15 interval, relating to the uncertainty in the eruption age of widespread tephra Ks11.     

230Th/234U and 14C dating of a lowstand coral reef beneath the insular shelf off Irabu Island, Ryukyus, southwestern Japan

Abstract   High-resolution seismic reflection profiles delineated the distribution of mound-shaped reflections, which were interpreted as reefs, beneath the insular shelf western off Irabu Island, Ryukyus, southwestern Japan. A sediment core through one of the mounded structures was recovered from the sea floor at a depth of −118.2 m by offshore drilling and was dated by radiometric methods. The lithology and coral fauna of the core indicate that the mounded structure was composed of coral–algal boundstone suggesting a small-scaled coral reef. High-precision α-spectrometric ²³⁰Th/²³⁴U dating coupled with calibrated accelerator mass spectrometric ¹⁴C ages of corals obtained reliable ages of this reef ranging from 22.18 ± 0.63 to 30.47 ± 0.98 ka. This proves that such a submerged reef was formed during the lowstand stage of marine oxygen isotope stages 3–2. The existence of low-Mg calcite in the aragonitic coral skeleton of 22.18 ± 0.63 ka provides evidence that the reef had once been exposed by lowering of the relative sealevel to at least −126 m during the last glacial maximum in the study area. There is no room for doubt that a coral reef grew during the last glacial period on the shelf off Irabu Island of Ryukyus in the subtropical region of western Pacific.     

Effect of depositional processes on the origin and composition of organic matter: Examples from the Pleistocene sediments in the Choshi core, Boso Peninsula

Abstract   Both marine and terrigenous organic matter are deposited in shelf and continental slope environments. In the present study, the relationship between environmental changes in the Choshi area and the sedimentation of organic matter was examined. The sediments of the Choshi core were deposited on a shelf environment and their lithology and ichnofacies, as well as the composition of the contained kerogen (insoluble organic matter) indicate a shallowing upward succession. The organic matter preserved in the sediments is of both marine and terrigenous origin, on the basis of C/N ratios (5.90–9.45), δ¹³C values (−21.6‰−24.6‰) and kerogen microscopy. The total organic carbon (TOC) content (0.39–1.08%) of the sediments shows a positive correlation with the increase of terrigenous organic matter before 500 ka, but decreases (0.26–0.61%) after 500 ka as the shelf environment becomes shallower because of dilution, caused by the input of terrigenous inorganic clasts, and oxidation. The variation in TOC contents was thus influenced by the increasing sedimentation rate of terrigenous materials, including both organic and inorganic particles as the basin filled.     

Origins of hydrocarbons in the Sagara oil field, central Japan

Abstract   We collected free-gas and in situ fluid samples up to a depth of 200.6 m from the Sagara oil field, central Japan (34°44'N, 138°15'E), during the Sagara Drilling Program (SDP) and measured the concentrations and stable carbon isotopic compositions of CH₄ and C₂H₆ in the samples. A combination of the CH₄/C₂H₆ ratios with the carbon isotope ratios of methane indicates that the hydrocarbon gases are predominantly of thermogenic origin at all depths. The isotope signature of hydrocarbon gases of δ¹³      < δ¹³     suggests that these gases in the Sagara oil field are not generated by polymerization, but by the decomposition of organic materials.     

Stable Isotopes (δ18O, δ2H) of Pore Waters in Clay-Rich Aquitards: A Comparison and Evaluation of Measurement Techniques

Pore water collected from piezometers installed in a thick clay-rich till were used to compare and evaluate four techniques for obtaining δD and δ¹⁸O values in these media. The techniques included mechanical squeezing, centrifugation, azeotropic distillation, and a direct soil-water equilibration technique. Direct CO₂-core equilibration yielded sufficiently accurate and reproducible δ¹⁸O results of pore water in clay-rich tills. In addition, this method eliminated the need for labor-intensive complete extraction of water from the geologic media. Mechanical squeezing and centrifugation produced results similar to direct equilibration. However, both of these methods exhibited a greater degree of variability and were laborious and more time consuming. Small differences in δ¹⁸O values between piezometer water and equilibrated, squeezed, and centhfuged samples suggested that each method collected different fractions of the clay-water reservoir. Although these subtle differences were not conclusive, they did suggest the presence of weakly bound water and highlighted the difference between these three techniques for determining the stable isotopic composition of pore water in clay-rich aquitards. Azeotropic distillation produced a high level of discrepancy in δD andδ¹⁸O results compared to the other methods. Incomplete extraction was considered the most probable cause of this error. The results of this study suggested that direct equilibration is the best method for determining detailed δD and δ¹⁸O values of pore water in clay-rich aquitards.     

Implication of the temporal sulphur isotopic variation during the 2000 eruption of Miyakejima Volcano, Japan

Abstract   The variation of sulphur isotopic composition during the 2000 eruption of the Miyakejima Volcano was examined in order to monitor the temporal change of the volcanic activity. The δ³⁴S values of water-soluble sulphate leached from volcanic ash effused during intermittent eruptions from July to September 2005 range from +5 to +11‰ with a fluctuation of ca 3‰ within a single eruption. The δ³⁴S value of sulphuric acid mist collected with 'Cu-metal trap' placed on the flank of the volcano from December 2000 to January 2001 is +6.2‰. These sulphur isotopic compositions of sulphate, which were isotopically equilibrated in the subvolcanic hydrothermal system, indicate that the temperature of the hydrothermal system beneath the caldera increased after the period of intermittent phreatic and phreatomagmatic eruptions. Then, the δ³⁴S value of sulphuric acid trapped from January to March 2001 was +9.0‰ and the δ³⁴S value of water-soluble sulphate on volcanic ash emitted with minor eruption in May 2001 was +11.0‰, suggesting a decrease in temperature of the subvolcanic hydrothermal system.     

Geographical distribution of helium isotope ratios in northeastern Japan

In order to study the precise geographical distribution of helium isotope ratios in northeastern Japan and compare it with geophysical data, we collected 43 gas and water samples from hot and mineral springs in the region where the ratio had never been reported, and measured the ³He/⁴He and ⁴He/²⁰Ne ratios of these samples. It was found that the ³He/⁴He ratios show clear contrasts between the forearc and the back-arc regions in the Tohoku district in northeastern Japan. In the forearc region, the ratios are smaller than 1 R_A (1 R_A = 1.4 × 10⁻⁶; R_A means the ³He/⁴He ratio of the atmosphere). On the other hand, those along the volcanic front and in the back-arc region are apparently higher. Moreover, we found a variation in the ³He/⁴He ratios along the volcanic front. In Miyagi Prefecture (38–39°N), the ratios range from 2 to 5 R_A. On the other hand, the ratios are less than 1 R_A in and around the southern border between Iwate and Akita Prefectures (39–39.5°N). Comparing the distribution of helium isotope ratios to results of recent geophysical studies, we found that the features in geographical distribution of helium isotope ratios are similar to those of seismic low-velocity zone distributions and high Qp⁻¹ distributions in the uppermost mantle. These observations strongly suggest that the helium isotope ratios reflect the distribution of melts in the uppermost mantle and are a useful tool for investigating the origin, behavior, and distribution of deep fluids and melts.     

Tracing coalbed natural gas-coproduced water using stable isotopes of carbon

Recovery of hydrocarbons commonly is associated with coproduction of water. This water may be put to beneficial use or may be reinjected into subsurface aquifers. In either case, it would be helpful to establish a fingerprint for that coproduced water so that it may be tracked following discharge on the surface or reintroduction to geologic reservoirs. This study explores the potential of using δ¹³C of dissolved inorganic carbon (DIC) of coalbed natural gas (CBNG)–coproduced water as a fingerprint of its origin and to trace its fate once it is disposed on the surface. Our initial results for water samples coproduced with CBNG from the Powder River Basin show that this water has strongly positive δ¹³C_DIC (12‰ to 22‰) that is readily distinguished from the negative δ¹³C of most surface and ground water (−8‰ to −11‰). Furthermore, the DIC concentrations in coproduced water samples are also high (more than 100 mg C/L) compared to the 20 to 50 mg C/L in ambient surface and ground water of the region. The distinctively high δ¹³C and DIC concentrations allow us to identify surface and ground water that have incorporated CBNG-coproduced water. Accordingly, we suggest that the δ¹³C_DIC and DIC concentrations of water can be used for long-term monitoring of infiltration of CBNG-coproduced water into ground water and streams. Our results also show that the δ¹³C_DIC of CBNG-coproduced water from two different coal zones are distinct leading to the possibility of using δ¹³C_DIC to distinguish water produced from different coal zones.     

Fukutoku-oka-no-ba Volcano: A new perspective on the Alkalic Volcano Province in the Izu–Bonin – Mariana arc

Pumice samples from Fukutoku-oka-no-ba in the Izu–Bonin – Mariana (IBM) arc were analysed for 40 trace elements and Sr, Nd, and Pb isotopic compositions. These samples are shoshonites (59.4–61.8 wt% SiO₂), characterized by high contents of K₂O (3.74–4.64 wt%), Ba (1274–1540 p.p.m.), Rb (91–105 p.p.m.), and light rare earth elements. The characteristics of alkali-element enrichment are similar to those of other parts of the Alkalic Volcano Province (AVP) in the northern Mariana and southernmost Volcano arcs. Sr (⁸⁷Sr/⁸⁶Sr = 0.7036–0.7038) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 19.08–19.11, ²⁰⁷Pb/²⁰⁴Pb = 15.62–15.63, ²⁰⁸Pb/²⁰⁴Pb = 38.85–38.91) of Fukutoku-oka-no-ba pumice are relatively radiogenic, whereas Nd is unradiogenic (¹⁴³Nd/¹⁴⁴Nd = 0.51283–0.51286). Fukutoku-oka-no-ba is isotopically distinct from Iwo Jima and is similar to the Hiyoshi Volcanic Complex, suggesting that Fukutoku-oka-no-ba might have a magma source similar to that of the Hiyoshi volcanic complex. Plots of Pb and Nd isotopes for AVP lavas trend toward the fields of ocean island basalt (OIB) source and pelagic sediments, which are possible sources of AVP enrichments.     

K–Ar and 40Ar/39Ar phengite ages of Sanbagawa schist clasts from the Kuma Group, central Shikoku, southwest Japan

Conglomerates of the Kuma Group, central Shikoku, southwest Japan contain Sanbagawa schist clasts with a variety of metamorphic grades and lithologies. K–Ar and ⁴⁰Ar/³⁹Ar dating of phengite show all the pelitic schist clasts from low- to high-grade zones have similar phengite ages (82–84 Ma) that are significantly older than those from the in situ Sanbagawa sequence of central Shikoku. This is because the Kuma–Sanbagawa sequence was exhumed earlier than the in situ Asemi sequence with an exhumation process intermediate between those for the Kanto Mountains and the in situ Asemi sequences. ⁴⁰A/³⁹Ar plateau ages (103 and 117 Ma) of phengite in amphibolites indicate the timing of the early stage of the exhumation of the metamorphic pile, probably close to the peak metamorphic age.     

Nitrate Source Identification Using δ15N in a Ground Water Plume Near an Intensive Swine Operation

Nitrate-contaminated ground water beneath and adjacent to an intensive swine ( Sus scrofa domesticus ) production facility in the Middle Coastal Plain of North Carolina was analyzed for δ¹⁵N of nitrate (δ¹⁵N-NO₃). Results show that the isotopic signal of animal waste nitrogen is readily identifiable and traceable in nitrate in this ground water. The widespread land application of animal wastes from intensive livestock operations constitutes a potential source of nitrogen contamination to natural water throughout large regions of the United States and other countries. The site of the present study has been suspected as a nitrate contamination source to nearby domestic supply wells and has been monitored for several years by government and private water quality investigators through sampling of observation wells, ditches, and streams. δ¹⁵N of nitrate allowed direct identification of animal waste-produced nitrate in 11 of 14 wells sampled in this study, as well as recognition of nitrate contributions from non-animal waste agricultural sources in remaining wells.     

Sulfur isotopic characteristics of late Cenozoic ore deposits at the arc junction of Hokkaido, Japan

Abstract Sulfide minerals of late Cenozoic vein-type deposits of southwest Hokkaido and Kuril Islands yielded δ³⁴_CDT S values of 2 to 8 permil, which are typical green-tuff values of magnetite-series igneous terrane. Sulfides of the Kitami district of northeast Hokkaido, on the other hand, are characterized by negative δ³⁴S_CDT values, ranging from 0 to - 7 permil. This unique value among ore deposits in the late Cenozoic back-arc terranes in the Japanese Islands is considered to have resulted from extraction of ³²S enriched sulfur from the basement rocks, because of well-developed N-S fracturing in the basement, which is characteristic of the axial belt and Kitami district of Hokkaido.     

The Matsue Formation: Evidence for gross mantle heterogeneity beneath Southwest Japan at 11 Ma

Abstract Middle Miocene basalts and basaltic andesites of the Matsue Formation outcrop within a 5 km radius of Matsue city in eastern Shimane Prefecture. Despite their limited outcrop and age (11.0 ± 1.5 Ma), they show a wide range in ⁸⁷Sr-⁸⁶Sr(0.70370–0.70593), ¹⁴³Nd-¹⁴⁴Nd(0.512904–0.512471) and large ion lithophile element (LILE) contents, but a relatively narrow range for some high field strength elements (HFSE) such as Nb and Ti. These basalts and andesites can be divided into three groups based on petrography, major element, trace element and isotope chemistry. Although one group has undergone some fractional crystallization, isotope chemistry precludes linkage of the groups by a closed-system process. Crustal contamination can explain isotope chemistry, but is not consistent with trace element variations. The most satisfactory model is eruption of two compositionally distinct magmas, with limited magma mixing and fractional crystallization. Published experimental work shows that one end-member resulted from shallow melting of upwelling mantle at ∼25 km. The simultaneous eruption of the other end member magma in the same area points towards a heterogeneous mantle. The isotopic composition of Matsue Formation basalts and andesites covers the entire range of Late Miocene mafic volcanic rocks of southwest Japan. Such gross heterogeneity developed on a local scale has implications for models that deal with regional chemical variations of mafic volcanic rocks in southwest Honshu.     

Primordial helium isotope signature from Plio–Quaternary alkaline basalts in Yemen

Abstract Isotopic compositions of He, Ne and Ar were measured on Plio–Quaternary alkaline basalts of Marib–Sirwah and Shuqra volcanic fields in Yemen, south-western Arabian Peninsula. Very high ³He/⁴He isotope ratios were found in olivine phenocrysts of some Quaternary alkaline basalts in both volcanic fields, located on the margin of the dispersed Afar mantle plume, compared with the Afar–Ethiopian province in the center of the mantle plume. This suggests that the Afar mantle plume source may consist of common component (C or focal zone (FOZO)) with variable primordial ³He/⁴He ratio rather than high μ mantle (HIMU) component. The three component mixing C as the Afar mantle plume, depleted mantle (DM) as upper mantle and lithospheric mantle with a hybrid enriched mantle I–II (EM I–EM II) characteristics may be adequate to explain He–Sr–Nd–Pb isotope variation for the Afar–Arabian Cenozoic volcanics. The occurrence of high ³He/⁴He ratios in the Marib–Sirwah volcanic field appears to show that the primitive basaltic magma, derived from the margin of the dispersed trous-like Afar mantle plume during 15–0 Ma, was not by contamination of lithospheric and upper mantle materials in comparison with that from the center of the Afar mantle plume as a result of relatively low thermal anomaly.     

Noble gases in pillow basalt glasses from the northern Mariana Trough back-arc basin

Noble gas concentrations and isotopic compositions have been measured in eight samples of pillow basalt glasses collected from seven different localities along 250 km of the Mariana Trough spreading and rifting axis. The samples have uniform and mid-ocean ridge basalt (MORB)-like ³He/⁴He values of 9–12 × 10^–6 (6.4–8.6 times atmospheric) despite large variations in ⁴He. Concentrations of the noble gases Ne, Ar, Kr, and Xe show much smaller variations between samples, but larger variations in isotopic compositions of Ne, Ar, and Xe. Excess radiogenic ²¹Ne is observed in some samples. ⁴⁰Ar/³⁶Ar varies widely (atmospheric to 1880). Kr is atmospheric in composition for all samples. Some samples show a clear excess ¹²⁹Xe, which is a well-known MORB signature. Isotopic compositions of the heavier noble gases (Ar, Kr, and Xe) in some samples, however, show more atmospheric components. These data reflect the interaction of a MORB-like magma with an atmospheric component such as seawater or of a depleted mantle source with a water-rich component that was probably derived from the subducting slab.     

Hydrothermal alteration of green tuff belt, Japan: Implications for the influence of seawater/volcanic rock interaction on the seawater chemistry at a back-arc basin

Abstract Chemical data on hydrothermally altered volcanic rocks from a green tuff belt in Japan indicate that the average rate of Mg removal from seawater due to seawater cycling through back-arc basins in the circum-Pacific region during the early to middle Miocene (25–15 Ma) is estimated to be 2.6±1 × 10¹³ g/year. This is similar to that through present-day mid-ocean ridges (2.4 × 10¹³ g/year). Hydrothermal fluxes of K, Ca and Si are calculated to be 4.2±1.6 × 10¹³ g/year, 4.3±1.7×10¹³ g/year and 1.0±0.4 × 10¹⁴ g/year, respectively. These calculated results indicate that the seawater/volcanic rocks interaction at subduction-related tectonic settings have to be taken into account in considering the geochemical mass balance of seawater over geologic time.     

40Ar/39Ar ages of blueschist facies pelitic schists from Qingshuigou in the Northern Qilian Mountains, western China

Abstract   Pelitic schists from Qingshuigou in the Northern Qilian Mountains of China contain mainly glaucophane, garnet, white mica, clinozoisite, chlorite and piemontite. Isotopic age dating of these schists provides new constraints on the formation of the high-grade blueschists at Qingshuigou. White mica ⁴⁰Ar/³⁹Ar ages range from 442.1 to 447.5 Ma (total fusion age of single grain) and from 445.7 to 453.9 Ma (integrated age of white mica concentrates). These ages (442.1–453.9 Ma) represent the peak metamorphic ages or cooling ages of the blueschists during exhumation shortly after peak metamorphism. The ⁴⁰Ar/³⁹Ar dates in the present study are similar to ages previously reported for eclogites and blueschists in the area; this suggests that both the eclogites and pelitic sediments underwent high-grade metamorphism during the same subduction event. From this chronological evidence and the presence of well-developed Silurian remnant-sea flysch and Devonian molasse, it is concluded that the Northern Qilian Ocean had closed by the end of the Ordovician, and rapid orogenic uplift followed in the Devonian.     

Geochemistry of geopressured hydrothermal waters in the Niigata Sedimentary Basin, Japan

Abstract   Geothermal waters in the Niigata Sedimentary Basin, central Japan, are divided into four groups based on their chemical composition (i.e. Na-SO₄-type, Na-SO₄-Cl-type, Na-Cl-type and Na-Cl-HCO₃-type). The Na-SO₄-type geothermal water forms as a consequence of water–rock interaction and generally occurs in the outer part of the basin. The Na-Cl-type geothermal water is further subdivided into the original Na-Cl-type geopressured thermal water and the mixed Na-Cl-type geothermal water, in terms of its geochemical and isotopic composition. The original Na-Cl-type geopressured thermal water originates from a geopressured hydrothermal system containing the altered fossil formation waters that are sealed at depth. It moves up to the upper part of the depositional succession or the ground, and generally does not mix with groundwater that is of meteoric origin. This type of water is cooled by heat conduction. The concentration of Cl^– in this type of thermal water is very similar to that in seawater. The δD and δ¹⁸O values are approximately constant and independent of temperature. The original Na-Cl-type geopressured thermal water is distributed mainly along anticlinal axes in folded Neogene formations. The mixed Na-Cl-type geothermal water is related to the expulsion activity of the geopressured hydrothermal system and occurs mostly along active faults. It is formed by shallow groundwater of meteoric origin being mixed with geopressured hydrothermal water when the geopressured hydrothermal system was expulsed along active faults by paroxysmal tectonic events.     

Correlation between the bedded chert sequence of southwest Japan and δ13C excursion of carbonate sequence, and its significance to the Permian-Triassic mass extinction

Abstract Stratigraphic productivity variations of radiolarians below the Permian-Triassic boundary are examined with Ishiga Diagrams in bedded chert sequences of southwest Japan. The diagrams of two different outcrops, drawn from the thickness variation of chert beds, show common stratigraphic variation, which indicates the diagram is a useful tool for correlation of bedded chert sequence. The common stratigraphic productivity variation is also well correlated to a compiled δ¹³C excursion of shallow carbonate sequences. Bedded chert records a dramatic extinction event in a shallow surface zone of oceans below the Permian-Triassic boundary. The Permian-Triassic mass extinction is divided into three intervals based on the Ishiga Diagrams, the stratigraphic lithological variation of bedded chert sequences, and the δ¹³C curve. The preceding extinction interval in the late Djulfian stage was not as serious an event and the biosphere soon recovered. The event of the main extinction interval commenced in the Dorashamian stage and caused a serious destruction of the biosphere. An event of the aftermath interval during the Early Triassic caused a delay in the recovery from the main extinction interval.     

Growth history and formation environments of ferromanganese deposits on the Philippine Sea Plate, northwest Pacific Ocean

Abstract   Hydrogenetic ferromanganese crusts are widespread on the floor of the northwestern Pacific Ocean, south and east of the Japanese Islands, despite vigorous tectonic activity, such as subduction and back-arc spreading, since at least the Mid-Paleogene over the Philippine Sea Plate region and nearby. The crusts occur mainly at water depths shallower than 3000 m, but also at greater depths of up to 6000 m. Fine-scale ¹⁰Be/⁹Be dating was undertaken on several 5–10 cm thick hydrogenetic ferromanganese crusts sampled from different geological environments, including inactive submarine volcanoes, tectonic escarpments and abandoned rifts. The results indicate that the crusts have grown at relatively constant rates of 4–7 mm/my without any significant time breaks. These uniform and constant growth rates suggest that the basins have been exposed constantly to oxygenated bottom waters since their formation in the Middle Miocene ( ca 15 Ma) or earlier. Local geological or oceanographic environmental changes might have slowed or increased some of the growth rates resulting in correlation of some internal structures. The Philippine Sea Plate region could have economic potential in areas of thick hydrogenetic ferromanganese crusts over a wide range of water depths.