GPS-measured land subsidence in Ojiya City, Niigata Prefecture, Japan

Land subsidence caused by compression of clay layers in Ojiya City, Japan was measured by global positioning system (GPS) between 1 April 1996 and 31 December 1998.

Three baselines were selected in and around the city, and height difference on a WGS-84 ellipsoid was measured by GPS on each baseline. The ground at the GPS station in the city subsides and rebounds 7 cm every winter and spring, respectively. Measurement accuracy was 9.5 mm standard deviation. Ground water level was observed at a well near the GPS station. Regression analysis between total strain, calculated as ratio of the height difference displacement to the total thickness of the clay layers, and the layers' effective stress change with ground water level change gave good correlation. The slope of regression line 7.0×10⁻¹¹ m²/N was obtained as an average apparent coefficient of volume compressibility of the layers.     

Ce and Nd isotope geochemistry on island arc volcanic rocks with negative Ce anomaly: existence of sources with concave REE patterns in the mantle beneath the Solomon and Bonin island arcs

¹³⁸Ce/¹⁴²Ce isotope ratios in Cenozoic island arc volcanic rocks are reported for the first time, together with isotope ratios of Nd and Sr and abundances of REE, Ba and Sr. The island arc volcanics studies here are boninites from Chichijima, the Bonin Islands, and basalts and andesites from the Solomon Islands. REE patterns of the island arc volcanic rocks from the Solmon Islands and the Bonin Islands are confirmed to have negative Ce anomalies. It is also disclosed that the majority of these island arc volcanic rocks show mainly positive values for both _Ce and _Nd. It is shown that these _Ce and _Ce values can hardly be interpreted by simple mixing between MORB and oceanic or continental crustal rocks; the former have positive _Nd and negative _Ce and the latter have negative _Ce and positive or negative _Nd. Existence of sources having positive _Ce and _Nd values is strongly suggested. If the sources are assumed to have been fractionated from CHUR (chondritic uniform reservoir) at the early or middle Precambrian era, the sources from which the volcanics were derived are concluded to have kept concave REE patterns with larger (La/Ce)_N and smaller (Nd/Sm)_N ratios than chondritic values over a substantial period of time, until the time of Cenozoic magmatism forming island arc volcanic rocks in question. During the periods of the Cenozoic magmatic activities and their related events, Ce anomalies are considered to have been created. From Ce and Nd isotope ratios, however, it is difficult to determine which of the following processes was responsible for the Ce anomaly; the incorporation process of subducted oceanic crust into magma at the mantle or the slab dehydration and metasomatism process. Nevertheless, so far as Ce and Nd isotopic ratios are concerned, incorporation of oceanic sediments did not take place to any clearly detectable degree.     

Pressure dependence on partition coefficients for trace elements between olivine and the coexisting melts

Partition coefficients between olivine and melt at upper mantle conditions, 3 to 14 GPa, have been determined for 27 trace elements (Li, Be, B, Na, Mg, Al, Si, P, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Rb, Sr, Y, Zr, Cs, Ba, La and Ce) using secondary-ion mass-spectrometry (SIMS) and electron-probe microanalysis (EPMA). The general pattern of olivine/melt partitioning on Onuma diagrams resembles those reported previously for natural systems. This agreement strongly supports the argument that partitioning is under structural control of olivine even at high pressure. The partition coefficients for mono- and tri-valent cations show significant pressure dependence, both becoming larger with pressure, and are strongly correlated with coupled substitution into cation sites in the olivine structure. The dominant type of trace element substitution for mono- and tri-valent cations into olivine changes gradually from (Si, Mg)↔(Al, Cr) at low pressure to (Si, Mg)↔(Al, Al) and (Mg, Mg)↔(Na, Al) at high pressure. The change in substitution type results in an increase in partition coefficients of Al and Na with pressure. An inverse correlation between the partition coefficients for divalent cations and pressure has been observed, especially for Ni, Co and Fe. The order of decreasing rate of partition coefficient with pressure correlates to strength of crystal field effect of the cation. The pressure dependence of olivine/melt partitioning can be attributed to the compression of cation polyhedra induced by pressure and the compensation of electrostatic valence by cation substitution. Received: March 6, 1997 / Revised, accepted: March 12, 1998     

U-Pb and Pb-Pb ages of zircons from basaltic eucrites: Implications for early basaltic volcanism on the eucrite parent body

We have undertaken petrologic and SHRIMP U-Th-Pb isotopic studies on zircons from basaltic eucrites (Yamato [Y]-75011, Y-792510, Asuka [A]-881388, A-881467 and Padvarninkai) with different thermal and shock histories. Eucritic zircons are associated with ilmenite in most cases and have subhedral shapes in unmetamorphosed and metamorphosed eucrites. Some zircons in highly metamorphosed eucrites with granulitic texture occur alone in pyroxene, and typically have rounded to subrounded shapes due to recrystallization. Superchondritic Zr/Hf ratios of eucritic zircons indicate that they crystallized from incompatible element-rich melts after crystallization of ilmenite. Concentrations of uranium and thorium in zircons in the unmetamorphosed eucrite Y-75011 are higher than those in metamorphosed eucrites.The U-Pb systems of eucritic zircons are almost concordant but some zircon grains show reverse discordance. Radiogenic lead-loss up to 48% from zircons is observed in the shock-melted eucrite Padvarninkai. The ²⁰⁷Pb-²⁰⁶Pb ages of zircon in Y-75011 (4550 ± 9 Ma, n = 5) are nearly identical, within analytical uncertainty, to the ages of zircons from the metamorphosed eucrite Y-792510 (4545 ± 15 Ma, n = 13), the highly metamorphosed eucrites A-881388 (4555 ± 54 Ma, n = 5) and A-881467 (4558 ± 13 Ma, n = 8), and the shock-melted eucrite Padvarninkai (4555 ± 13 Ma, n = 18). The averaged ²⁰⁷Pb-²⁰⁶Pb age of zircon from five eucrites analyzed in this study is 4554 ± 7 Ma (95% confidence limits, n = 49), indistinguishable from the averaged U-Pb age (4552 ± 9 Ma) of the same samples. Because of the high closure temperature of lead in zircon (T_closure = ∼1050°C with a cooling rate of 0.2°C/yr), the ²⁰⁷Pb-²⁰⁶Pb ages of eucritic zircon do not represent metamorphic ages but crystallization ages of extrusive lavas.This fact strongly suggests that volcanism of the eucrite parent body occurred at a very early stage of the Solar System history, 7-20 Ma after CAI formation (4567.2 ± 0.6 Ma), thus basaltic eucrites crystallized from parental magmas within a short interval following the differentiation of their parent body. The U-Pb ages of eucritic zircons are older than the U-Pb, Sm-Nd and Rb-Sr ages of some basaltic eucrites, which is consistent with differences in closure temperatures of each isotopic system, and suggests that thermal and shock metamorphism affected the isotopic systems of pyroxene, plagioclase and phosphates.     

Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems

The rates of chemical reactions between aqueous sulfates and sulfides are essentially identical to sulfur isotopic exchange rates between them, because both the chemical and isotopic reactions involve simultaneous oxidation of sulfide-sulfur atoms and reduction of sulfate-sulfur. The rate of reaction can be expressed as a second order rate law: R = k·[∑SO₄^2?]·[∑S^2?], where R is the overall rate, k is the rate constant and [∑SO₄^2?] and [∑S^2?] are molal concentrations. We have computed the rate constants from the available experimental data on the partial exchange of sulfur isotopes between aqueous sulfates and sulfides using the rate law established by us: $\text{ln(}\text{α}{}^{\mathrm{e}}\text{? α}\text{α}{}^{\mathrm{e}}\text{? α}{}^0\text{) = ? kt([∑SO}{}_4{}^{\mathrm{2?}}\text{] + [∑S}{}^{\mathrm{2?}}\text{])}$, where t is time and α⁰, α, and α^e are, respectively, the fractionation factors at t = 0 (the initial condition), at the end of experiment, and at equilibrium. The equilibrium fractionation factor can be expressed as: $\text{1000 ln α}{}^{\mathrm{e}}\text{=}\text{6.463 × 10}{}^6\text{T}{}^2\text{+ 0.56 (±.5)}$ (T in Kelvin).The rate constants are strongly dependent on T and pH, but not in as simple a manner as suggested by Igumnov (1976). Our rate constants in Na-bearing hydrothermal solutions decrease by 1 order of magnitude with an increase in pH by 1 unit at pH's less than ~3, remain constant in the pH range of ~4 to ~7, and again decrease at pH >7. The activation energy for the reaction also depends on pH: 18.4 ± 1 kcal/mole at pH = 2, 29.6 ± 1 kcal/mole at pH = 4 to 7, and between 40 and 47 kcal/mole at pH around 9. The observed pH dependence of the rate constant and of the activation energy can be best explained by a model involving thiosulfate molecules as reaction intermediates, in which the intramolecular exchange of sulfur atoms in thiosulfates becomes the rate determining step.The rate constants obtained in this study were used to compute the changes in the isotopic fractionation factors between aqueous sulfates and sulfides during cooling of fluids. Comparisons with data of coexisting sulfate-sulfide minerals in hydrothermal deposits, suggest that simple cooling was not a likely mechanism for coprecipitation of sulfate and sulfide minerals at temperatures below 350°C. Mixing of sulfide-rich solutions with sulfate-rich solutions at or near the depositional sites is a more reasonable process for explaining the observed fractionation.The degree of attainment of chemical equilibrium between aqueous sulfates and sulfides in a hydrothermal system, and the applicability of a_O2-pH type diagrams to mineral deposits, depends on the ∑S content and the thermal history of the fluid, which in turn is controlled by the flow rate and the thermal gradient in the system.The rates of sulfate reduction by non-bacterial processes involving a variety of reductants are also dependent on T, pH, [∑SO₄^2?], and [∑S^2?], and appear to be fast enough to become geochemically important at temperatures above about 200°C.     

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

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.     

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.     

Response analysis of the Higashi–Kobe Bridge and surrounding soil in the 1995 Hyogoken–Nanbu Earthquake

This paper presents results of observation and analysis of the response of one of the longest cable-stayed bridges in the world to the Hyogoken–Nanbu (Kobe) Earthquake of 17 January 1995. It is determined that interaction of the foundations of the bridge towers with the supporting soil plays a decisive role in the overall structural behaviour. The key factor governing the changes of the soil properties at this site is pore-water pressure buildup, which results in liquefaction of the saturated surface soil layers under large dynamic loads. Models of the soil and structure are created and initially validated by accurately simulating the system response to a small earthquake. Soil parameters reflecting the pore-water pressure buildup in the strong earthquake are determined by an advanced non-linear effective stress analysis, combining the Ramberg–Osgood model of stress–strain dependence with a pore pressure model based on shear work concept. They are utilized to investigate and simulate the interaction of the foundation and the supporting soil using the program SASSI with the flexible volume substructuring approach. The results show a good agreement with the observations and have useful implications to the scientific and engineering practice. © 1998 John Wiley & Sons, Ltd.     

Simulations of seasonal variations of sulfur compounds in the remote marine atmosphere

A photochemical box model is used to simulate seasonal variations in concentrations of sulfur compounds at latitude 40° S. It is assumed that the hydroxyl radical (OH) addition reaction to sulfur in the dimethyl sulfide (DMS) molecule is the predominant pathway for methanesulfonic acid (MSA) production, and that the rate constant increases as the air temperature decreases. Concentration of the nitrate radical (NO₃) is a function of the DMS flux, because the reaction of DMS with NO₃ is the most important loss mechanism of NO₃. While the diurnally averaged concentration of OH in winter is a factor of about 8 smaller than in summer, due to the weak photolysis process, the diurnally averaged concentration of NO₃ in winter is a factor of about 4–5 larger than in summer, due to the decrease of DMS flux. Therefore, at middle and high latitudes in winter, atmospheric DMS is mainly oxidized by the reaction with NO₃. The calculated ratio of the MSA to SO₂ production rates is smaller in winter than in summer, and the MSA to non-sea-salt sulfate (nssSO₄ ^2-) molar ratio varies seasonally. This result agrees with data on the seasonal variation of the MSA/nssSO₄ ^2- molar ratio obtained at middle and high latitudes. The calculations indicate that during winter the reaction of DMS with NO₃ is likely to be a more important sink of NO_x (NO+NO₂) than the reaction of NO₂ with OH, and to serve as a significant pathway of the HNO₃ production. If dimethyl sulfoxide (DMSO) is produced through the OH addition reaction and is heterogeneously oxidized in aqueous solutions, half of the nssSO₄ ^2- produced in summer may be through the oxidation process of DMSO. It is necessary to further investigate the oxidation products by the reaction of DMS with OH, and the possibility of the reaction of DMS with NO₃ during winter.     

Seasonal variations of spectra of wind speed and air temperature in the mesoscale frequency range

Seasonal variations of the spectra of wind speed and air temperature in the mesoscale frequency range from 1.3 × 10^-4 to 1.5 × 10^-3 Hz (10 min to 2 h periods) have been studied through observations over land for one year. Spectrographs [time series of isopleths of spectral densities, f · S(f) vs f] of wind speed and air temperature contain occasional peaks that are attributed to short-lived mesoscale atmospheric activity with narrow frequency bands. Significant spectral peaks of wind speed were found in 19% of the total observations in winter, and in 15–16% in the other seasons; for air temperature, they occured in 12% of observations in autumn, and in 16–19% in the other seasons. The peaks most often occurred in the period range from 30 min to 1 h; most had durations less than 24 h. Mesoscale fluctuations of wind speed and air temperature were highly correlated, and in most cases, phase differences were 90–180 ° with air temperature leading wind speed. Significant spectral peaks of wind speed often occurred during northerly seasonal cold winds in winter, and accompanied tropical and/or mid-latitude cyclones in the other seasons. When the peaks occurred, wind speed was usually relatively high and the atmospheric surface layer was unstable.