Depositional and diagenetic history of limestones and dolostones of the Oligo‐Miocene Kujung Formation in the Northeast Java Basin,Indonesia

Lithological and geochemical features of platformal carbonates record the signatures of the global climates and the regional environmental settings and also reconstruct the diagenetic history and porosity evolution, which are essential to evaluate the potential of hydrocarbon reservoirs. This study investigates the platformal carbonates of the Oligo‐Miocene Krunji Formation of North East Java Basin, which are potentially significant hydrocarbon reservoirs. The carbonate sequence in a 283 m thick section at Kranji in East Java is subdivided into three lithological units: limestone unit 1, dolostone unit 2, and limestone unit 3, in ascending order. The strontium‐isotope ratios of well‐preserved calcite samples indicate the depositional period from Chattian (late Oligocene) to Burdigalian (early Miocene), which is consistent with ages of the foraminifer assemblages. Unit 1 consists of low‐porosity limestone, in which two horizons of subaerial exposure are recognized by the occurrence of red‐colored matrix and lower δ¹³C values. Unit 2 consists of dolomitic rock and exhibits coarse‐grained calcitic grains and cross‐stratified structure. Considering that this unit has been subject to dolomitization, the sediment of unit 2 was initially permeable and was likely deposited in a shoal setting. The overlying unit 3 of Aquitanian–Burdigalian age is characterized by a highly granular texture. High porosity and uniformly low δ¹³C and δ¹⁸O values indicate that Unit 3 was subjected to more intense meteoric diagenesis than the Chattian unit 1. This was likely a consequence of the Antarctic ice‐sheet expansion during the Oligocene/Miocene transition, which amplified sea level change. The unit 2 dolomite has high δ¹³C and δ¹⁸O values and a high ⁸⁷Sr/⁸⁶Sr ratio which resulted from the reflux of seawater into permeable the sediment body in middle‐late Miocene (Burdigalian Tortonian) following the deposition of unit 3. The porosity and permeability of the Kujung Formation were initially controlled by sedimentological processes, but largely modified by later diagenetic processes.     

Natural and experimental structural evolution of dispersed organic matter in mudstones: The Shimanto accretionary complex,southwest Japan

Structural changes induced by thermal maturation of dispersed organic matter (OM) in the Shimanto accretionary complex, southwest Japan, were investigated using micro‐Fourier‐transform infrared spectroscopy and micro‐Raman spectroscopy. Natural dispersed OM exhibits systematic structural changes inferred from D1‐ and G‐band FWHM values, Raman band separation (RBS), and intensity ratios of the D1‐ and G‐bands (I_D1/I_G ratio) from diagenetic zone to anchizone (IC values: 0.75–0.30). Infrared spectra indicate a loss of aliphatic CH _x, aromatic CH _x, and oxygen‐containing structures as temperature increases. These changes are consistent with discontinuities in thermal structures bounded by out‐of‐sequence thrusts. Kinetic pyrolysis experiments indicate that the I_D1/I_G ratio of synthesized OM has a power law relationship with heat treatment time. Kinetic models of temperature dependence were fitted using the I_D1/I_G ratio, and an effective activation energy of 106 ±17 kJ/mol was estimated using an Arrhenius equation. The activation energies estimated by power law rate and Avrami models have a least‐square correlation coefficient of 0.93, indicating the temperature dependence of carbonization. The estimated effective activation energy is consistent with that of coal, lignin, cellulose, and hemicellulose during thermal degradation. On the other hand, RBS, and D1‐ and G‐band FWHM values of OM display more complex changes with increasing heating temperature and time, and it is difficult to constrain rate parameters during pyrolysis experiments. Our data indicate that the I_D1/I_G ratio is controlled by a simple thermally activated process, whereas RBS and D1‐ and G‐band FWHM values can be affected by lithostatic pressure, fluid activity, hydrogen index, and host lithology, as well as temperature. Structural evolution of dispersed OM in mudstones differs between natural and anhydrous closed experimental systems. Natural carbonization based on micro‐Raman spectroscopy should be applied for a limited indicator of thermal maturation, especially for dispersed OM in diagenetic zone.     

Subhorizontal boundary between ultrahigh-pressure and low-pressure metamorphic units in the Sulu–Tjube area of the Kokchetav Massif, Kazakhstan

Abstract The Kokchetav Massif of Kazakhstan includes high to ultrahigh-pressure (HP–UHP) metamorphic rocks (some of which were recrystallized at depths in excess of 150 km), juxtaposed against much lower pressure metamorphic components. We investigated the relationship between the HP–UHP metamorphic unit and the low pressure (LP) unit (Daulet Suite) in the Sulu–Tjube area, where the metamorphic rocks have previously been interpreted as constituting a megamelange with subvertical structural attitudes. Analyses of fold structures suggest that the HP–UHP metamorphic unit overlies the LP unit across a west-dipping subhorizontal boundary. In addition, kinematic indicators display top-to-the-north senses of shear along the tectonic contact between the two units, indicating that the HP–UHP unit has been extruded northward onto the LP unit. Following the juxtaposition of the two units, upright folds developed in both units, and these are associated with the previously reported steeply dipping metamorphic foliations. These data have important implications for the mode of exhumation of the UHP rocks from upper mantle to shallow crustal depths.     

Nickel–bearing Djerfisherite in Gehlenite-Spurrite Skarn at Kushiro, Hiroshima Prefecture, Japan

Abstract: Djerfisherite occurs intimately intergrown with troilite and pentlandite in gehlenite-spurrite skarn at Kushiro, mainly as inclusions in gehlenite and andradite grains. The mode of occurrence indicates that the djerfisherite formed in the culminated stage of the contact metamorphic-metasomatic process. The chemical compositions of the mineral are approximately represented by a formula of K₆Na(Fe, Ni, Cu)₂₄S₂₆Cl with Ni up to 4. 85. It is likely that high temperature condition corresponding to the formation of gehlenite-spurrite skarn as well as low f_O2 and f_S2 conditions are responsible for the formation of djerfisherite in the potassium-rich chemical environments.     

Small-Amplitude Disturbances in a Radiating and ScatteringGrey MediumI. Solutions of Given Real Frequency ω

We reanalyze the propagation of one-dimensional small-amplitude disturbances of given real frequency ω in a radiating and scattering grey medium using the Eddington approximation, which has been studied previously by us (Kaneko et al., 1976). Numerical results reveals three frequency regimes to be distinguished, and two wave modes always appear in each frequency regime. The governing equations and analytic solutions are derived for all wave modes using Whitham's method modified into quadratic form and approximate methods based on radiation thermodynamics. In the high-frequency regime appear the radiation-wave and adiabatic sound modes, which are damped by opacity and radiative cooling, respectively. Wave patterns in the intermediate-frequency and low-frequency regimes depend critically on the importance of radiation, for which the criterion is given in terms of the ratio of total specific heats at constant pressure and constant volume. When the radition overwhelms the matter (radiation-dominated case), the radiative mode in the intermediate-frequency regime is the constant-volume diffusion mode. When the matter overwhelms the radiation (matter-dominated case), damped radiation-wave and damped radiation-diffusion modes newly appear between the radiation-wave and constant-volume diffusion modes. The acoustic mode in the intermediate-frequency regime is the isothermal sound mode,which is damped by radiative cooling at higher frequencies and by radiation-thermal drag force at lower frequencies. Two modes appearing in the low-frequency regime are the isentropic radiation-acoustic and constant-pressure diffusion modes. The absorption coefficient derived for the former is shown to be a radiation-thermodynamic extension of that of Landau and Lifshitz (1987). The transition frequencies between all adjacent two modes are also derived to discuss the implications of them. This revised version was published online in July 2006 with corrections to the Cover Date.     

Estimation and Projection of Non-Linear Relative Sea-Level Rise in the Seto Inland Sea,Japan

Future sea-level rise (SLR) in and around the Seto Inland Sea (SIS), Japan, is estimated in 2050 and 2100 using ensemble empirical mode decomposition (EEMD) and long-term sea-level records. Ensemble empirical mode decomposition, an adaptive data analysis method, can separate sea-level records into intrinsic mode functions (IMFs) from high to low frequencies and a residual. The residual is considered a non-linear trend in the sea-level records. The mean SLR trend at Tokuyama in the SIS from EEMD is 3.00?mm?y^?1 from 1993 to 2010, which is slightly lower than the recent altimetry-based global rate of 3.3?±?0.4?mm?y^?1 during the same period. Uncertainty in SLR is estimated by considering interdecadal variations in the sea levels. The resulting SLR in 2050 and 2100 for Tokuyama is 0.19?±?0.06?m and 0.56?±?0.18?m, respectively. The stations along the coast of the Pacific Ocean display a greater and more rapid SLR in 2100 compared with other stations in the SIS. The SLR is caused not only by mass and volume changes in the sea water but also by other factors, such as local subsidence, tectonic motion, and river discharge. The non-linear trend of SLR, which is the residual from EEMD, is interpreted as the sum of the local factors that contribute to the sea-level budget.     

A Study on the Formation of Smectite in Silica Scales Precipitated from Geothermal Water: The Effect of Magnesium

Abstract. Silica scales containing large amounts of smectite were recently found in the pipelines for geothermal water at a geothermal power plant. To elucidate the mechanism of smectite formation, seven silica scale samples were characterized by powder X-ray diffraction, chemical analysis and ²⁷A1 MAS NMR. Smectite was present in samples with MgO levels above 10 wt% and Al₂O₃ levels below 10 wt%. In ²⁷A1 MAS NMR spectra, peaks assigned to both tetrahedrally and octahedrally coordinated aluminum (Al(4) and Al(6)) were observed for Mg-rich samples, whereas a peak due to Al(4) alone appeared in Mg-poor samples. From these observation and comparison between ²⁷A1 MAS NMR spectra for synthesized precipitates of Al₂O₃-SiO₂ containing MgO and not containing MgO, it is concluded that magnesium plays an important role in the stabilization of Al(6), and results in the formation of smectite     

Nitrate pollution of groundwater in the Yellow River delta,China

Nitrate pollution of groundwater in the Yellow River delta, China is an important issue related not only to nitrate dispersion and health concerns but also to mass transport and interactions of groundwater, sea, and river waters in the coastal area. The spatial distribution of nitrate, nitrate sources, and nitrogen transformation processes were investigated by field surveys and geochemical methods. Nitrate occurred mainly in shallow layers and had a spatial distribution coinciding with geomorphology and land/water use. Irrigation water from the Yellow River and anthropogenic waste are two main nitrogen sources of nitrate in the delta, and both denitrification and mixing processes could take place according to characteristics identified by ionic and isotopic data.     

Nitrate pollution from agriculture in different hydrogeological zones of the regional groundwater flow system in the North China Plain

A survey of the quality of groundwater across a broad area of the North China Plain, undertaken in 1998 to 2000, indicates that nitrate pollution is a serious problem affecting the drinking water for a vast population. The use of nitrogen (N)-fertilizer in agriculture has greatly increased over the past 20 years to meet the food needs of the rapidly expanding population. During the study, 295 water samples were collected from wells and springs to determine the water chemistry and the extent of nitrate pollution. High concentrations of nitrate, especially in a recharge area along the western side, but also in the vicinity of Beijing and locally in other parts of the plain, pose a serious problem for the drinking water supply. In places, the nitrate concentration exceeds the maximum for safe drinking water of 45 mg/L. The intense use of N-fertilizer and the widespread use of untreated groundwater for crop irrigation contribute greatly to the problem, but no doubt the disposal of industrial and municipal waste into streams and infiltrating the aquifer also contribute to the problem; however, the lack of data prevents evaluation of those sources. In the recharge area, nitrate is found at depths of as much as 50 m. Near Beijing, relatively high concentrations of nitrate occur at depths of as much as 80 m. In the discharge area, in the vicinity of the Yellow River, high concentrations of nitrate occur at depths of <8 m.

---

Electronic Supplementary Material Supplementary Material is available in the online version of this article at

---

Resumen Contaminacíon de nitratos a causa de prácticas agrícolas en diferentes zonas hidrogeológicas del sistema de flujo regional de aguas subterráneas en la planice del norte de China. Un estudio de la calidad del agua subterránea en una zona amplia de la planice del norte de China se llevó a cabo entre 1998 y el año 2000. Este estudio indica que la contaminación de nitratos es un problema grave que afecta el agua potable de una vasta población. El uso de fertilizantes a base de nitratos en la agricultura ha aumentado considerablemente durante los últimos 20 años para satisfacer las necesidades alimentices de la creciente población. Durante el estudio, se tomaron 295 muestras de pozos de agua y manantiales para determinar la química de las aguas y el grado de contaminación por nitratos. Altas concentraciones de nitratos, especialmente en una zona de recarga a lo largo del lado oeste, asì como en la cercanía a Pekín y en zonas locales en otras partes de la planicie, presentan un problema serio al sumunistro de agua potable. En ciertos lugares, la concentracióon de nitratos excede el nivel máximo de seguridad para el agua potable 45 mg NO₃/L. El intenso uso de fertilizantes de nitratos y el abundante uso de agua subterránea sin tratamiento para la irrigación de cultivos contribuyen sustancialmente al problema. Sin embargo, sin lugar a dudas, la descarga de deshechos industriales y municipales en arroyos y en el acuífero también contribuyen al problema. La falta de datos impide la evalución de dichas fuentes. En la zona de recarga se encuentran nitratos hasta los 50 m de profundidad. Cerca a Pekín, concentraciones relativamente altas de nitrato ocurren hasta los 80 m de profunidad. En las zonas de descarga afectadas por el Río Amarillo las concentraciones altas de nitrato se encuentran solamente a menos de 8m de profundidad.

---

Resumé Une campagne dévaluation de la qualité de leau souterraine entreprise entre 1998 et 2000 à travers une vaste étendue de la plaine du nord en Chine indique que la pollution par les nitrates est un problème sérieux qui affecte la qualité de leau souterraine pour une abondante population. Lutilisation de fertilisants azotés pour lagriculture a augmenté considérablement durant les 20 dernières années afin de rencontrer les besoins alimentaires dune population à forte croissance. Lors de cette étude, 295 échantillons deau ont été prélevés dans des puits et sources naturelles afin de déterminer la composition chimique de leau souterraine ainsi que létendue de la pollution par les nitrates. Des concentrations élevées de nitrates, en particulier dans une zone de recharge le long de la limite ouest de la plaine, mais aussi dans la région de Beijing et sporadiquement dans la plaine, posent de sérieux problèmes à la consommation de leau souterraine. A certains endroits, la concentration en nitrates excède la valeur maximale acceptée pour la consommation qui est de 45 mg NO₃/L. Lutilisation intensive de fertilisants azotés ainsi que lutilisation répandue deau souterraine non traitée pour lirrigation contribuent pour beaucoup au problème, mais il ne fait pas de doute que le rejet des déchets municipaux et industriels dans les rivières et aquifères y est aussi pour quelque chose. Par contre, le manque de donnés ne permet pas dévaluer la contribution de chacune de ces sources. Dans la zone de recharge, les nitrates se retrouvent à des profondeurs allant jusquà 50 m. Près de Beijing, des concentrations relativement élevées de nitrate ont été mesurées à des profondeurs allant jusquà 80 m. Enfin, dans la zone démergence affectée par la rivière Jaune, les fortes concentrations se retrouvent à une profondeur maximale de 8 m.

     

Another sea area separated from the Panthalassic Ocean in the Norian,the Late Triassic: The lowest Sr isotopic composition of the Ishimaki limestone in central Japan

Mt. Ishimaki is the Jurassic accretionary complex of the Chichibu Belt in Toyohashi City, near Nagoya in central Japan. The Ishimaki limestone is thought to be seamount-type limestone. The P₁ elements of the conodonts Norigondolella navicula and Ancyrogondolella quadrata found in the limestone indicate it is of Norian age. The Sr isotopic compositions of 45 Ishimaki limestone samples ranged from 0.7055 to 0.7077. Eighteen of these samples had lower Sr isotopic compositions than the lowest Sr isotopic composition (0.7068) of seawater throughout the Phanerozoic. The Sr isotopic compositions in the limestone block are generally lower at the base of the block and higher at the top. The present Sr isotopic compositions of the Ishimaki limestone are unlikely to have been reduced by post-depositional alteration because most of the limestone samples had a low amount of Mn (<300 ppm) or high Sr/Mn ratios (>2) and the conodont elements had low (1–2) CAI (conodont alteration index) values. Additionally, there was little acid-insoluble residue. Thus, the low Sr isotopic compositions are thought to represent the strontium of the past ambient seawater. The low Sr isotopic compositions are in complete disagreement with the generally recognised range of seawater Sr isotopic compositions in the Norian stage of the Late Triassic (0.7075–0.7078) because the depositional environment of the Ishimaki limestone was closed or semi-closed from the Panthalassic Ocean. Therefore, the Sr isotopic composition of the limestone differs from that of the Panthalassic seawater. The low Sr isotopic compositions were probably affected by Sr inflows from mafic oceanic crust by hydrothermal fluid circulation or from hinterlands surrounded by mafic rocks by river water circulation.