Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase     

Norimichi Takenaka  Tohru Daimon  Akihiro Ueda  Keiichi Sato  Masaru Kitano  Hiroshi Bandow  Yasuaki Maeda 《Journal of Atmospheric Chemistry》1998,29(2):135-150

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.  相似文献   

Trace element distribution in mineral separates of the Allende inclusions and their genetic implications     

Hiroshi Nagasawa  Douglas P Blanchard  Jeffrey W Jacobs  Joyce C Brannon  John A Philpotts  Naoki Onuma 《Geochimica et cosmochimica acta》1977,41(11):1587-1600

Concentrations of the REE, Sc, Co, Fe, Zn, Ir, Na and Cr were determined by instrumental neutron activation and mass spectrometric isotope dilution analysis for mineral separates of the coarseand fine-grained types (group I and II of Martin and Mason's classification) of the Allende inclusions.These data, combined with data on mineral/liquid partition coefficients, oxygen isotope distributions and diffusion calculations, suggest the following: (1) Minerals in the coarse-grained inclusions (group I) crystallized in a closed system with respect to refractory elements. On the other hand, differences in oxygen isotope distributions among minerals preclude a totally molten stage in the history of the inclusion. Group I inclusions were formed by rapid condensation (either to liquid or solid) in a supercooled solar nebula; extrasolar pyroxene and spinel dust were included but not melted in the condensing inclusions, thus preserving their extrasolar oxygen isotope composition. REE were distributed by diffusion during the subsequent heating at subsolidus temperatures; because oxygen diffuses much more slowly at these temperatures, the oxygen isotope anomalies were preserved. (2) The fine-grained (group II) inclusions were also formed by condensation from a super-cooled nebular gas; however, REE-rich clinopyroxene and spinel were formed early and REE-poor sodalite and nepheline were formed later and mechanically mixed with clinopyroxene and spinel to form the inclusions. The REE patterns of the bulk inclusions and the mineral separates are fractionated, indicating that REE abundances in the gaseous phase were already fractionated at the time of condensation of the minerals. (3) Pre-existing Mg isotope anomalies in the coarse-grained inclusions must have been erased during the heating stage thus resetting the ²⁶Al-²⁶Mg chronometer.  相似文献   

ESR diagram: a method to distinguish vitrinite macerals     

Hiroshi Morishima  Hideki Matsubayashi 《Geochimica et cosmochimica acta》1978,42(5):537-540

It has been found that samples consisting of a homogeneous vitrinite show a good ESR correlation of spin concentration with geothermal parameters and that a graph of ESR line width vs g-value can be useful in the identification of the maceral and the determination of the coalification rank.  相似文献   

The theory of the nutation for the rigid earth model at the second order   总被引：6，自引：0，他引：6  

Hiroshi Kinoshita  Jean Souchay 《Celestial Mechanics and Dynamical Astronomy》1990,48(3):187-265

We perform a complete reconstruction of the series of the nutation for a rigid Earth model with the use of the very accurate theories ELP2000 and VSOP82 for the motion of the Moon and the planets respectively, in such a way that all the individual contributions up to 0.005 mas should be taken. This implies the introduction of the planetary effects, of the influence of second-order parts of the potential of the Earth (J3, triaxiality), and some improvements due to an extension of the theory at the second order. All this increase notably the number of coefficients to be taken in account, and modifies also in a significant way the value of some of them.  相似文献   

From an initial transient-state to a steady-state in metamorphic reactions: An experimental approach in the system dolomite-quartz-H₂O     

Tadao  Nishiyama  Aiko  Tominaga  Hiroshi  Isobe 《Island Arc》2007,16(1):16-27

Abstract We carried out hydrothermal experiments in the system dolomite‐quartz‐H₂O to track the temporal change in reaction rates of simultaneous reactions during the development of reaction zones. Two types of configurations for the starting materials were prepared: dolomite single crystals + quartz powder + water and quartz single crystals + dolomite powder + water, both sealed separately in gold capsules. Runs at 0.1GPa and 600°C with cold seal pressure vessels gave the following results. (i) In short duration (45–71 h) runs metastable layer sequences involving wollastonite and talc occur in the reaction zone, whereas they disappear in longer duration (168–336 h) runs. (ii) The layer sequence of the reaction zones in short duration runs differs from place to place on the dolomite crystal even in the same run. (iii) The diversity of layer sequences in the short duration runs merges into a unique layer sequence in the longer duration runs. (iv) The reaction zone develops locally on the dolomite crystal, but no reaction zone was observed on the quartz crystal in any of the runs. The lines of evidence (i)–(iii) show that the system evolves from an initial transient‐ to a steady‐state and that the kinetic effect is important in the development of reaction zones. A steady diffusion model for the unique layer sequence Qtz/Di/Fo + Cal/Dol + Cal/Dol shows that the Dol + Cal layer cannot be formed by diffusion‐controlled process and that the stability of the layer sequence Qtz/Di/Fo + Cal/Dol depends not only on L‐ratios (a = /L_CaOCaO and b = /L_MgOMgO) but also on the relative rate P = (−2ξ₁ − ξ₂)/(–ξ₁ − 2ξ₂) of competing reactions: Dol + 2Qtz = Di + 2CO₂ (ξ₁) and 2Dol + Qtz = Fo + 2Cal + 2CO₂ (ξ₂). For smaller P the stability field will shift to higher values of a and b. The steady diffusion model also shows that the apparent‐non‐reactivity on the quartz surface can be attributed to void formation in a large volume fraction in the diopside layer.  相似文献   

High-resolution observations of dissolved isoprene in surface seawater in the Southern Ocean during austral summer 2010–2011     

Sohiko Kameyama  Satoshi Yoshida  Hiroshi Tanimoto  Satoshi Inomata  Koji Suzuki  Hisayuki Yoshikawa-Inoue 《Journal of Oceanography》2014,70(3):225-239

We measured dissolved isoprene (2-methyl-1,3-butadiene; C₅H₈) concentrations in a broad area of the southern Indian Ocean and in the Indian sector of the Southern Ocean from 35°S to 64°S and from 37°E to 111°E during austral summer 2010–2011. Isoprene concentrations were continuously measured by use of a proton-transfer-reaction mass spectrometer combined with a bubbling-type equilibrator. Concentrations of isoprene and its emission flux throughout the study period ranged from 0.2 to 395 pmol L^?1 and from 181 to 313 nmol m^?2 day^?1, respectively, the averages being generally higher than those of previous studies. Although we found a significant linear positive relationship between isoprene and chlorophyll-a concentrations (r ² = 0.37, n = 36, P < 0.001), the correlation coefficient was lower than previously reported. In contrast, in the high-latitude area (>53°S) we identified a significant negative correlation (r ² = 0.59, n = 1263, P < 0.001) between isoprene and the temperature-normalized partial pressure of carbon dioxide (n-pCO₂), used as an indicator of net community production in this study. This suggests that residence times and factors controlling variations in isoprene and n-pCO₂ are similar within a physically stable water column.  相似文献   

Large-Eddy Simulation of Pollutant Removal from a Three-Dimensional Street Canyon   总被引：3，自引：3，他引：0  

Takenobu Michioka  Hiroshi Takimoto  Ayumu Sato 《Boundary-Layer Meteorology》2014,150(2):259-275

Large-eddy simulations were conducted to investigate the mechanism of pollutant removal from a three-dimensional street canyon. Five block configurations with aspect ratios (building height to length) of 1, 2, 4, 8 and $\infty $ were used to create an urban-like array. A pollutant was released from a ground-level line source at the centre of the target canyon floor. For smaller aspect ratios, the relative contribution of the turbulent mass flux to net mass flux at the roof level, which was spatially averaged along the roof-level ventilation area, was closer to unity, indicating that turbulent motions mainly affected pollutant removal from the top of the canyon. As aspect ratio increased, the relative contribution became smaller, owing to strong upwind motions. However, the relative contribution again reached near unity for the infinite aspect ratio (i.e. a two-dimensional street canyon) because of lowered lateral flow convergence. At least 75 % of total emissions from the three-dimensional street canyon were attributable to turbulent motions. Pollutant removal by turbulent motions was related to the coherent structures of low-momentum fluid above the canyons. Though the coherent structure size of the low-momentum fluid differed, the positions of low-momentum fluid largely corresponded to instantaneous high concentrations of pollutant above the target canyon, irrespective of canyon geometry.  相似文献   

Solid‐state 13C NMR characterization of insoluble organic matter from Antarctic CM2 chondrites: Evaluation of the meteoritic alteration level     

Hikaru YABUTA  Hiroshi NARAOKA  Kinya SAKANISHI  Hiroyuki KAWASHIMA 《Meteoritics & planetary science》2005,40(5):779-787

Abstract— Chemical structures of the insoluble organic matter (IOM) from the Antarctic CM2 chondrites (Yamato [Y‐] 791198, 793321; Belgica [B‐] 7904; Asuka [A‐] 881280, 881334) and the Murchison meteorite were analyzed by solid‐state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Different types of carbons were characterized, such as aliphatic carbon (Ali‐C), aliphatic carbon linked to hetero atom (Hetero‐Ali‐C), aromatic carbon (Aro‐C), carboxyls (COOR), and carbonyls (C=O). The spectra of the IOM from Murchison and Y‐791198 showed two major peaks: Ali‐C and Aro‐C, while the spectra from the other meteorites showed only one major peak of Aro‐C. Carbon distribution was determined both by manual integration and deconvolution. For most IOM, the Aro‐C was the most abundant (49.8–67.8%) of all carbon types. When the ratios of Ali‐C to Aro‐C (Ali/Aro) were plotted with the atomic hydrogen to carbon ratio (H/C), a correlation was observed. If we use the H/C as a parameter for the thermal alteration event on the meteorite parent body, this result shows a different extent of thermal alteration. In addition, IOM with a lower Ali/Aro showed a lower ratio of Ali‐C to COOR plus C=O (Ali / (COOR + C=O)). This result suggests that the ratio of CO moieties to aliphatic carbon in IOM might reflect chemical oxidation that was involved in hydrothermal alteration.  相似文献   

Textural variations and impact history of the Millbillillie eucrite     

Akira Yamaguchi  Hiroshi Takeda  Donald D. Bogard  Daniel Garrison 《Meteoritics & planetary science》1994,29(2):237-245

Abstract— We have investigated 10 new specimens of the Millbillillie eucrite to study its textures and mineral compositions by electron probe microanalyser and scanning electron microscope. Although originally described as having fine-grained texture, the new specimens show diversity of texture. The compositions (Mg/Fe ratios) of the host pigeonites and augite lamellae are homogeneous, respectively, in spite of the textural variation. In addition to their chemical homogeneity, pyroxenes in coarse and fine-grained clasts are partly inverted to orthopyroxene. Chemical zoning of plagioclase during crystal growth is preserved. This eucrite includes areas of granulitic breccias and impact melts. Large scale textures show a subparallel layering suggesting incomplete mixing and deposition of impact melt and lithic fragments. An ³⁹Ar-⁴⁰Ar age determination for a coarse-grained clast indicates a strong degassing event at 3.55 ± 0.02 Ga. We conclude that Millbillillie is among the most equilibrated eucrites produced by thermal annealing after impact brecciation. According to the classification of impact breccias, Millbillillie can be classified as a mixture of granulitic breccias and impact melts. The last significant thermal event is characterized by network-like glassy veins that run through clasts and matrices. Consideration of textural observations and requirements for Ar-degassing suggests that the ³⁹Ar-⁴⁰Ar age could in principle date either the earilier brecciation and annealing event or the event which produced the veins.  相似文献   

A study of Mg and K isotopes in Allende CAIs: Implications to the time scale for the multiple heating processes     

Motoo Ito  Hiroshi Nagasawa  Hisayoshi Yurimoto 《Meteoritics & planetary science》2006,41(12):1871-1881

Abstract— The measurements of magnesium and potassium isotopic compositions of refractory minerals in Allende calcium‐aluminum‐rich inclusions (CAIs), 7R‐19–1, HN3–1, and EGG3 were taken by secondary ion mass spectrometry (SIMS). The 7R‐19–1 contains ¹⁶O‐rich and ¹⁶O‐poor melilite grains and define a single isochron corresponding to an initial ²⁶Al/²⁷Al ratio of (6.6 ± 1.3) × 10^?5. The Al‐Mg isochron, O isotope measurements and petrography of melilite in 7R‐19–1 indicate that ¹⁶O‐poor melilite crystallized within 0.4 Myr after crystallization of ¹⁶O‐rich melilite, suggesting that oxygen isotopic composition of the CAI‐forming region changed from ¹⁶O‐rich to ¹⁶O‐poor within this time interval. The ¹⁶O‐poor melilite is highly depleted in K compared to the adjacent ¹⁶O‐rich melilite, indicating evaporation during remelting of 7R‐19–1. We determined the isochron for ⁴¹Ca‐⁴¹K isotopic systematics in EGG3 pyroxene with (4.1 ± 2.0) × 10^?9 (2s?) as an initial ratio of ⁴¹Ca/⁴⁰Ca, which is at least two times smaller than the previous result (Sahijipal et al. 2000). The ratio of ⁴¹Ca/⁴⁰Ca in the EGG3 pyroxene grain agrees within error with the value obtained by Hutcheon et al. (1984). No evidence for the presence of ⁴¹K excess (decay product of a short‐lived radionuclide ⁴¹Ca) was found in 7R‐19–1 and HN3–1. We infer that the CAI had at least an order of magnitude lower than canonical ⁴¹Ca/⁴⁰Ca ratio at the time of the CAI formation.  相似文献