Geochemistry of gas hydrate accumulation offshore NE Sakhalin Island (the Sea of Okhotsk): results from the KOMEX-2002 cruise

Geochemical properties of gas hydrate accumulation associated with an active gas vent on the continental slope offshore northeast Sakhalin Island in the Sea of Okhotsk have been investigated. The pore water chemistry data suggest that the gas hydrates (GHs) were formed in an environment of upward-migrating fluid combined with a mechanism of pore water segregation. The upward infiltration of water enriched mainly by Cl^– and K⁺ species appears to occur on the background of earlier diagenesis processes within the gas vent sediments. The GHs were formed from water with chlorinity ranging from 530 to 570 mM. The ¹⁸O and D of GH water varied from –1.4 to –1.8 and from –13 to –18, respectively, representing a mix of seawater and infiltrating fluid water. A complex interaction of pore water, water of ascending fluid and segregated pore water during hydrate formation is also supported by water content measurements and observed gas hydrate structure. The direction of segregated water is opposite to upward fluid migration. Decreasing activity of the gas vent is inferred by comparing the present top of the recovered hydrate layer with previous observations.     

Halogen systematics in the Mallik 5L-38 gas hydrate production research well,Northwest Territories,Canada: Implications for the origin of gas hydrates under terrestrial permafrost conditions

The authors report here halogen concentrations in pore waters and sediments collected from the Mallik 5L-38 gas hydrate production research well, a permafrost location in the Mackenzie Delta, Northwest Territories, Canada. Iodine and Br are commonly enriched in waters associated with CH₄, reflecting the close association between these halogens and source organic materials. Pore waters collected from the Mallik well show I enrichment, by one order of magnitude above that of seawater, particularly in sandy layers below the gas hydrate stability zone (GHSZ). Although Cl and Br concentrations increase with depth similar to the I profile, they remain below seawater values. The increase in I concentrations observed below the GHSZ suggests that I-rich fluids responsible for the accumulation of CH₄ in gas hydrates are preferentially transported through the sandy permeable layers below the GHSZ. The Br and I concentrations and I/Br ratios in Mallik are considerably lower than those in marine gas hydrate locations, demonstrating a terrestrial nature for the organic materials responsible for the CH₄ at the Mallik site. Halogen systematics in Mallik suggest that they are the result of mixing between seawater, freshwater and an I-rich source fluid. The comparison between I/Br ratios in pore waters and sediments speaks against the origin of the source fluids within the host formations of gas hydrates, a finding compatible with the results from a limited set of ¹²⁹I/I ratios determined in pore waters, which gives a minimum age of 29 Ma for the source material, i.e. at the lower end of the age range of the host formations. The likely scenario for the gas hydrate formation in Mallik is the derivation of CH₄ together with I from the terrestrial source materials in formations other than the host layers through sandy permeable layers into the present gas hydrate zones.     

Deposition rates of polysilicic acid with up to 10 M calcium ions

Cementitious materials used for radioactive waste repository construction complicate the performance assessment of radioactive waste systems because the use of cement may greatly alter the pH (8–13) of groundwater and release constituents such as calcium ions. Under such conditions, it is important to clarify also the dynamic behavior of silica (silicic acid), in order to evaluate the alteration in the chemical and physical properties of the fractured layer or the host rock surrounding the repository. Since silica undergoes polymerization, precipitation or dissolution depending on the pH and/or temperature, the behavior of silica would be greatly complicated in the presence of other ions. This study is focused on the deposition rates of polysilicic acid and soluble silicic acid with up to 10⁻³ M Ca ions. In the experiment, Na₂SiO₃ solution (250 mL, pH > 10, 298 K) was poured into a polyethylene vessel containing amorphous silica powder (0.5 g), and a buffer solution, HNO₃, and CaNO₃ as Ca ions were sequentially added into the vessel. The pH of the solution was set to 8. The silica, initially in a soluble form at pH > 10 (1.4 × 10⁻² M), became supersaturated and either deposited on the solid surface or changed into the polymeric form. Then the concentrations of both poly- and soluble silicic acid were monitored over a 40-day period. The decrease of polysilicic acid became slow with an increase in the concentration of Ca ions in the range of up to 10⁻³ M. In general, the addition of electrolytes to a supersaturated solution accelerates the aggregation and precipitation of polymeric species. However, the experimental result showed that polysilicic acid in the presence of Ca ions is apparently stable in solution, compared with that under a Ca-free condition. On the other hand, the concentration of soluble silicic acid in the presence of Ca ions immediately became metastable, that is, slightly higher than the solubility of soluble silicic acid. Its dynamic behavior was similar to that in the Ca-free condition.     

Geochemical Process of Gas Hydrate Formation in the Nankai Trough Based on Chloride and Isotopic Anomalies in Interstitial Water

Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO₄²-, δ¹⁸O and δD. The baselines for the Cl- concentration and δ¹⁸O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ¹⁸O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in ¹⁸O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ¹⁸O anomalies gives results of up to 80 % in sand, and shows that the δ¹⁸O baseline is not consistent with the Cl" baseline. The δ¹⁸O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in ¹⁸O are responsible for the increase in the δ¹⁸O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.     

Geochemical Features of Vein Anhydrite from the Kakkonda Geothermal System, Northeast Japan

Abstract. Cathodoluminescence (CL) color, rare earth element (REE) content, sulfur and oxygen isotopes and fluid inclusions of anhydrite, which frequently filled in hydrothermal veins in the Kakkonda geothermal system, were investigated to elucidate the spatial, temporal and genetical evolution of fluids in the deep reservoir. The anhydrite samples studied are classified into four types based on CL colors and REE contents: type-N (no color), type-G (green color), type-T (tan color) and type-S (tan color with a high REE content). In the shallow reservoir, only type-N anhydrite is observed. In the deep reservoir, type-G anhydrite occurs in vertical veins whereas type-T and -N in lateral veins. Type-S anhydrite occurs in the heat-source Kakkonda Granite. The CL textures revealed that type-G anhydrite deposited earlier than type-T in the deep reservoir, implying that fracture system was changed from predominantly vertical to lateral.
Studies of fluid inclusions and δ³⁴S and δ¹⁸O values of the samples indicate that type-N anhydrite deposited from diluted fluids derived from meteoric water, whereas type-G, -T and -S anhydrites deposited from magmatic brines derived from the Kakkonda Granite with the exception of some of type-G with recrystallization texture and no primary fluid inclusion, which deposited from fossil seawater preserved in the sedimentary rocks. Type-G, -T and -S anhydrites exhibit remarkably different chondrite-normalized REE patterns with a positive Eu anomaly, with a convex shape (peak at Sm or Eu) and with a negative Eu anomaly, respectively. The difference in the patterns might result from the different extent of hydrothermal alteration of the reservoir rocks and contribution of the magmatic fluids.     

Active strike–slip faulting and macroscopically nonrigid deformation of volcanic rocks in central Japan inferred from a paleomagnetic study

Detailed paleomagnetic investigation of a pyroclastic flow deposit has clarified the deformation mode around an active fault. In central Japan, the early Quaternary Nyukawa Pyroclastic Flow Deposit is cut by the active dextral Enako fault. Activity level of the fault is evaluated on the basis of geological and geomorphological surveys. Then, paleomagnetic samples are collected from 22 sites at exposures located on a lineament that is adjoining and parallel to the Enako fault. Stable thermoremanent magnetization (TRM) of the pyroclastic deposit is isolated through progressive thermal and/or alternating field demagnetization tests. Untilted site-mean directions of the TRMs simultaneously acquired during initial cooling indicate significant clockwise vertical-axis rotation. The lineament was then activated with right-lateral motions through the early Quaternary. Together with the late Quaternary activities along the adjoining Enako fault evaluated by our study, the present result exemplifies a migration of active segments within a fault system during the Quaternary. Paleomagnetic directions on the strike–slip fault are not concordant with uniform deformation predicted by the model of rotation of rigid blocks aligned on a master fault, but suggestive of a periodic deformation as a result of intense fracturing and differential rotation of blocks bounded by nested parallel faults.     

Developing a hybrid multi‐model for peak flood forecasting

The present study aims to develop a hybrid multi‐model using the soft computing approach. The model is a combination of a fuzzy logic, artificial neural network (ANN) and genetic algorithm (GA). While neural networks are low‐level computational structures that perform well dealing with raw data, fuzzy logic deal with reasoning on a higher level by using linguistic information acquired from domain experts. However, fuzzy systems lack the ability to learn and cannot adjust themselves to a new environment. Moreover, experts occasionally make mistakes and thus some rules used in a system may be false. A network type structure of the present hybrid model is a multi‐layer feed‐forward network, the main part is a fuzzy system based on the first‐order Sugeno fuzzy model with a fuzzification and a defuzzification processes. The consequent parameters are determined by least square method. The back‐propagation is applied to adjust weights of network. Then, the antecedent parameters of the membership function are updated accordingly by the gradient descent method. The GA was applied to select the fuzzy rule. The hybrid multi‐model was used to forecast the flood level at Chiang Mai (under the big flood 2005) and the Koriyama flood (2003) in Japan. The forecasting results are evaluated using standard global goodness of fit statistic, efficient index (EI), the root mean square error (RMSE) and the peak flood error. Moreover, the results are compared to the results of a neuro‐genetic model (NGO) and ANFIS model using the same input and output variables. It was found that the hybrid multi‐model can be used successfully with an efficiency index (EI) more than 0·95 (for Chiang Mai flood up to 12 h ahead forecasting) and more than 0·90 (for Koriyama flood up to 8 h ahead forecasting). In general, all of three models can predict the water level with satisfactory results. However, the hybrid model gave the best flood peak estimation among the three models. Therefore, the use of fuzzy rule base, which is selected by GA in the hybrid multi‐model helps to improve the accuracy of flood peak. Copyright © 2009 John Wiley & Sons, Ltd.     

Oligocene crustal xenolith‐bearing alkaline basalt from Jandaq area (Central Iran): implications for magma genesis and crustal nature

The Oligocene alkaline basalts of Toveireh area (southwest of Jandaq, Central Iran) exhibit northwest–southeast to west–east exposure in northwest of the central‐east Iranian microcontinent (CEIM). These basalts are composed of olivine (Fo_70–90), clinopyroxene (diopside, augite), plagioclase (labradorite), spinel, and titanomagnetite as primary minerals and serpentine and zeolite as secondary ones. They are enriched in alkalis, TiO₂ and light rare earth elements (La/Yb = 9.64–12.68) and are characterized by enrichment in large ion lithophile elements (Cs, Rb, Ba) and high field strength elements (Nb, Ta). The geochemical features of the rocks suggest that the Toveireh alkaline basalts are derived from a moderate degree partial melting (10–20%) of a previously enriched garnet lherzolite of asthenospheric mantle. Subduction of the CEIM confining oceanic crust from the Triassic to Eocene is the reason of mantle enrichment. The studied basalts contain mafic‐ultramafic and aluminous granulitic xenoliths. The rock‐forming minerals of the mafic‐ultramafic xenoliths are Cr‐free/poor spinel, olivine, Al‐rich pyroxene, and feldspar. The aluminous granulitic xenoliths consist of an assemblage of hercynitic spinel + plagioclase (andesine–labradorite) ± corundum ± sillimanite. They show interstitial texture, which is consistent with granulite facies. They are enriched in high field strength elements (Ti, Nb and Ta), light rare earth elements (La/Yb = 37–193) and exhibit a positive Eu anomaly. These granulitic xenoliths may be Al‐saturated but Si‐undersaturated feldspar bearing restitic materials of the lower crust. The Oligocene Toveireh basaltic magma passed and entrained these xenoliths from the lower crust to the surface.