Effect of divalent cations on the kinetics of Fe(III) complexation by organic ligands in natural waters     

Manabu Fujii  Andrew L. Rose  Tatsuo Omura 《Geochimica et cosmochimica acta》2008,72(5):1335-1349

We have investigated the kinetics of Fe(III) complexation by several organic ligands including fulvic acid, citrate and ethylenediaminetetraacetic acid (EDTA). Particular attention was given to examination of the effect of competitive divalent cations (Me: Ca²⁺ and Mg²⁺) at concentrations typical of seawater on the complexation rate. All experiments were conducted in 0.5 M NaCl solution buffered with 2 mM bicarbonate at pH 8.0 in the absence and presence of Me (25 μM-250 mM). The rate constants of complex formation determined by using the competitive ligand (5-sulfosalicylic acid) method combined with visible spectrophotometry ranged from 3.3 × 10⁴ to 3.2 × 10⁶ M⁻¹ s⁻¹. The mechanism of complexation was then examined based on a kinetic model. When EDTA was used as a ligand, Me at concentrations comparable to the ligand markedly retarded the rate of iron complex formation due to the predominance of an adjunctive pathway (where iron-ligand complex is formed via direct association of iron to Me-ligand complex). In contrast, the competing effect of Me on iron complexation by citrate and fulvic acid was observed only when the Me concentration was in excess of the ligand by more than a factor of 10-1000. The kinetic model suggests that iron complexation by fulvic acid occurs predominantly via a disjunctive pathway (where iron complexation by ligand occurs after dissociation of Me from Me-ligand complex) at concentrations of divalent cations and natural organic matter typical of natural waters including seawater and freshwater.  相似文献   

Sound velocity and elastic properties of Fe–Ni and Fe–Ni–C liquids at high pressure     

Soma Kuwabara  Hidenori Terasaki  Keisuke Nishida  Yuta Shimoyama  Yusaku Takubo  Yuji Higo  Yuki Shibazaki  Satoru Urakawa  Kentaro Uesugi  Akihisa Takeuchi  Tadashi Kondo 《Physics and Chemistry of Minerals》2016,43(3):229-236

The sound velocity (V _P) of liquid Fe–10 wt% Ni and Fe–10 wt% Ni–4 wt% C up to 6.6 GPa was studied using the ultrasonic pulse-echo method combined with synchrotron X-ray techniques. The obtained V _P of liquid Fe–Ni is insensitive to temperature, whereas that of liquid Fe–Ni–C tends to decrease with increasing temperature. The V _P values of both liquid Fe–Ni and Fe–Ni–C increase with pressure. Alloying with 10 wt% of Ni slightly reduces the V _P of liquid Fe, whereas alloying with C is likely to increase the V _P. However, a difference in V _P between liquid Fe–Ni and Fe–Ni–C becomes to be smaller at higher temperature. By fitting the measured V _P data with the Murnaghan equation of state, the adiabatic bulk modulus (K _S0) and its pressure derivative (K _S ^′ ) were obtained to be K _S0 = 103 GPa and K _S ^′  = 5.7 for liquid Fe–Ni and K _S0 = 110 GPa and K _S ^′  = 7.6 for liquid Fe–Ni–C. The calculated density of liquid Fe–Ni–C using the obtained elastic parameters was consistent with the density values measured directly using the X-ray computed tomography technique. In the relation between the density (ρ) and sound velocity (V _P) at 5 GPa (the lunar core condition), it was found that the effect of alloying Fe with Ni was that ρ increased mildly and V _P decreased, whereas the effect of C dissolution was to decrease ρ but increase V _P. In contrast, alloying with S significantly reduces both ρ and V _P. Therefore, the effects of light elements (C and S) and Ni on the ρ and V _P of liquid Fe are quite different under the lunar core conditions, providing a clue to constrain the light element in the lunar core by comparing with lunar seismic data.  相似文献   

CFC Indicating Renewal of the Japan Sea Deep Water in Winter 2000–2001     

Shizuo Tsunogai  Kentaro Kawada  Shuichi Watanabe  Takafumi Aramaki 《Journal of Oceanography》2003,59(5):685-693

The distributions of CFC (chlorofluorocarbon) in the water column was determined twice in 2000 and 2001 in the northwestern Japan Sea. In 2000 the CFC-11 concentration decreased almost exponentially with depth from 6 pmol/kg at a few hundred m deep to 0.3 pmol/kg or less at the bottom of about 3400 m depth at three stations (40–41°N, 132–133°E) about 300 km off Vladivostok. In 2001 the CFC-11 concentration increased sharply up to 2 pmol/kg in the bottom water, while it did not increase at a station (42.0°N, 136.5°E) about 450 km away to the northeast. This is due to the renewal of the bottom water which is replaced by the surface water flowing down along the continental slope, as suggested by Tsunogai et al. (1999), who proposed the continental shelf pump. Furthermore, an increase in the CFC-11 concentration was observed throughout the entire water column above 3000 m depth, although the proportion of the increase was about 20%, which was one order of magnitude smaller than that in the bottom water. The increase in inventory is almost four times larger than that in the bottom water below 3000 m depth which is equivalent to about 1/6 of the total inventory found in 2000. The increase also means that 3% of the deep water was replaced by the recent surface water, or, if the turnover occurs every year, that the turnover time of the deep water to be about 30 years. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

Highly alkaline,high-temperature hydrothermal fluids in the early Archean ocean     

Takazo Shibuya  Tsuyoshi Komiya  Kentaro Nakamura  Ken Takai  Shigenori Maruyama 《Precambrian Research》2010

Based on the petrology of hydrothermally altered Archean basaltic greenstones, thermodynamic calculations of phase equilibria were conducted to estimate the composition of a high-temperature (∼350 °C) hydrothermal fluid in an Archean subseafloor basalt-hosted hydrothermal system. The results indicate that the hydrothermal fluid was highly alkaline attributed to the presence of calcite in the alteration minerals under a high-CO₂ condition, and predict a generation of SiO₂-rich, Fe-poor hydrothermal fluids in the Archean subseafloor hydrothermal system. The chemically reactive mixing zones between alkaline hydrothermal fluids and slightly acidic-neutral seawater are characterized by inverse pH and chemical polarity to modern hydrothermal systems, leading to extensive precipitation of silica and iron oxyhydroxides on/under the seafloor. Such processes can be responsible for the abiotic formation of voluminous chert and subseafloor silica dike, the mechanism of silicification, and the pH-controlled generation of banded iron formation that has been arising mainly from the redox chemistry in the Archean ocean. Such high-temperature alkaline fluids could have had a significant role not only in the early ocean geochemical processes but also in the early evolution of life.  相似文献   

Interstadial coral reef terraces and relative sea-level changes during marine oxygen isotope stages 3–4, Kikai Island, central Ryukyus, Japan     

Keiichi Sasaki  Akio Omura  Kazuo Murakami  Natsume Sagawa  Toru Nakamori 《Quaternary International》2004,120(1):51

Coral reef terraces are one of the best recorders of relative sea-level changes during the last glacial cycle. Thus far, knowledge of relative sea-level record based on coral reefs during the marine Oxygen Isotope Stage (OIS) 3 has been limited to studies of the Huon Peninsula, Papua New Guinea. High-precision a α-spectrometric ²³⁰Th/²³⁴U dating demonstrated an offlapping sequence of five coral reef complexes, ages of which are 66, 64, 62, 55 and 52 ka, in the northern part of Kikai Island, central Ryukyus of Japan. Interstadial reefs, characterized by deepening-upward sequences of coral assemblages, recorded three hemicycles from transgression to highstand at 52, 62, and 66 ka, during which these reefs were drowned. These highstands in the relative sea-level record can be correlated with the eustatic record reconstructed from the Huon reef terraces and with the interstadials 14, 18, and 19 of the GISP 2 oxygen isotope record. This consistency confirms the Huon sea-level record of OIS 3 and implies that the eustatic sea level responded to the millennial-scale climate changes even during the glacial period of OIS 4.  相似文献   

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

Keiichi  Sasaki  Akio  Omura  Tetsuo  Miwa  Yoshihiro  Tsuji  Hiroki  Matsuda  Toru  Nakamori  Yasufumi  Iryu  Tsutomu  Yamada  Yuri  Sato  Hiroshi  Nakagawa 《Island Arc》2006,15(4):455-467

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.  相似文献   

Three‐dimensional microstructure of samples recovered from asteroid 25143 Itokawa: Comparison with LL5 and LL6 chondrite particles     

Akira Tsuchiyama  Masayuki Uesugi  Kentaro Uesugi  Tsukasa Nakano  Ryo Noguchi  Toru Matsumoto  Junya Matsuno  Takashi Nagano  Yuta Imai  Akira Shimada  Akihisa Takeuchi  Yoshio Suzuki  Tomoki Nakamura  Takaaki Noguchi  Masanao Abe  Toru Yada  Akio Fujimura 《Meteoritics & planetary science》2014,49(2):172-187

In this study, the three‐dimensional (3‐D) microstructure of 48 Itokawa regolith particles was examined by synchrotron microtomography at SPring‐8 during the preliminary examination of Hayabusa samples. Moreover, the 3‐D microstructure of particles collected from two LL6 chondrites (Ensisheim and Kilabo meteorites) and an LL5 chondrite (Tuxtuac meteorite) was investigated by the same method for comparison. The modal abundances of minerals, especially olivine, bulk density, porosity, and grain size are similar in all samples, including voids and cracks. These results show that the Itokawa particles, which are surface materials from the S‐type asteroid Itokawa, are consistent with the LL chondrite materials in terms of not only elemental and isotopic composition of the minerals but also 3‐D microstructure. However, we could not determine whether the Itokawa particles are purely LL5, LL6, or a mixture of the two. No difference between the particles collected from Rooms A and B of the sample chamber, corresponding to the sampling sequence of the spacecraft's second and first touchdowns, respectively, was detected because of the statistically small amount of particles from Room B.  相似文献   

Detection of Pacific tropical water variability by taut-line moorings in the western equatorial Pacific   总被引：1，自引：0，他引：1  

Iwao Ueki  Kentaro Ando 《Journal of Oceanography》2013,69(4):429-441

This study uses temperature and salinity time series acquired with taut-line moorings in the western equatorial Pacific to investigate water mass behavior on the thermocline layer. Basically, it is insufficient to trace water mass variation by the original discrete depth coordinate data because of relatively high variability of density at fixed depth near the thermocline. A reconstruction method based on the density surface motion caused by tidal forcing was used to derive continuous profiles of temperature and salinity from vertically discrete measurements at fixed depths. This method can represent detailed vertical salinity structures and their variation, especially along the potential density surface of 24.8σ_θ, where the salinity maximum of South Pacific tropical water (SPTW) appeared. Variability around the 24.8σ_θ surface at each site was as large as that observed at the surface, which suggests a strong influence of SPTW behavior. High salinity along the 24.8σ_θ surface within the equatorial band of the western Pacific appeared during boreal fall-winter at sites far from New Guinea. In contrast, high salinity appeared near New Guinea during the boreal spring-summer. These features suggest the influence of the New Guinea Coastal Undercurrent. Over longer time scales, several higher salinity events were observed. The most pronounced salinity event occurred during 2007–2008. Interannual variation of the salinity anomaly along the 24.8σ_θ surface was negatively correlated with the Niño 3.4 sea surface temperature anomaly. A long-term salinity anomaly shift from negative to positive occurred around the end of 2002. The relationship with decadal variation in subtropical cell transport is also discussed.  相似文献   

Fifteen years progress of the TRITON array in the Western Pacific and Eastern Indian Oceans     

Kentaro Ando  Yoshifumi Kuroda  Yosuke Fujii  Tatsuya Fukuda  Takuya Hasegawa  Takanori Horii  Yasuhisa Ishihara  Yuji Kashino  Yukio Masumoto  Keisuke Mizuno  Motoki Nagura  Iwao Ueki 《Journal of Oceanography》2017,73(4):403-426

The Triangle Trans‐Ocean Buoy Network (TRITON) project by the Japan Agency for Marine-Earth Science and Technology began with deployment in the western tropical Pacific Ocean in 1998 and has shifted to steady, long-term observations since 1999. After on-site inter-comparison with the Autonomous Temperature Line Acquisition System mooring system of the Tropical Atmosphere and Ocean (TAO) array by the National Oceanic and Atmospheric Administration, the TRITON array became the international TAO/TRITON array in 2000 as a key component of the Global Ocean and Climate Observing Systems. The TAO/TRITON array took over from the TAO array, which was developed during the Tropical Ocean and Global Atmosphere program (1985–1994), and replaced the western part of TAO with new additional real-time measurements of salinity and ocean currents. In 2001, two TRITON moorings were deployed in the eastern Indian Ocean for capturing the eastern pole of the Indian Ocean Dipole. From this initiative, the Indian Ocean Observing System (IndOOS) was designed, and the Indian Ocean mooring array (Research Moored Array for Africa–Asian–Australian Monsoon Analysis and Prediction) was developed as a key component of IndOOS. In this paper, 15 years of progress in the TRITON project in the western Pacific and eastern Indian Oceans is reviewed with regards to scientific outcomes, technological development, and collaborations with international and domestic partners. Future directions for sustainable observation in the Pacific and Indian Oceans are also discussed.  相似文献   

Geochemical characteristics of zircons in the Ashizuri A‐type granitoids: An additional granite topology tool for detrital zircon studies          下载免费PDF全文

Yusuke Sawaki  Kazue Suzuki  Hisashi Asanuma  Satoki Okabayashi  Kentaro Hattori  Takuya Saito  Takafumi Hirata 《Island Arc》2017,26(6)

Zircon is resistant to alteration over a wide range of geological environments, and isotopic ratios within the mineral provide constraints on ages and their parental magmas. Trace element compositions in zircon are also expected to reflect those of their parent magmas, and have a potential as essential indicators for their host rocks. Because most detrital zircons that accumulate at river mouths are derived primarily from granitoids, the classification of zircon within granitoids is potentially meaningful. This study employs the conventional classification scheme of granites (I‐, S‐, M‐, and A‐types). To clarify geochemical characteristics of zircons in A‐type granites, trace element compositions of zircons extracted from the A‐type Ashizuri granitoids were examined. Zircons from the Ashizuri granitoids commonly show enrichments of heavy rare earth elements and positive Ce anomalies, indicating that these zircons were igneous in origin. In addition, zircons in these A‐type granites are characterized by enrichments of Nb, Y, Ta, Th, and U and strong negative Eu anomalies, which exhibit good positive correlations with those in their whole rocks. This fact indicates that these signatures in zircons reflect well those in their parental bodies and are useful in identifying zircons derived from A‐type granite. Based on compilations of available data, zircons from A‐type granites can be clearly discriminated from other‐types of granites within Nb/Sr–Eu anomaly, U/Sr–Eu anomaly, Nb/Sr–U/Sr, and Nb/Sr–Ta/Sr cross‐plots. All indices used in these diagrams were selected based on the geochemical features of both zircon and whole rock of A‐type granites. Application of these discrimination diagrams to detrital zircons will likely provide further insights. For example, some Hadean detrital zircons plot in similar fields to A‐type granites, implying the existence of A‐type magmatism in the Earth's earliest history.  相似文献