Paleomagnetism of the Cu�CZn�CPb-bearing Kupferschiefer black shale (Upper Permian) at Sangerhausen, Germany

Syngenetic, diagenetic and epigenetic models have been proposed for the Cu?CZn?CPb Kupferschiefer mineralization at Sangerhausen, Germany. Paleomagnetic and rock magnetic measurements have been made on 205 specimens from mine workings on the margin of the Sangerhausen Syncline. The mineralization is richest in the ??0.5-m-thick Upper Permian (258?±?2?Ma) Kupferschiefer black marly shale (nine sites) and dies out over ??0.2?m in the underlying Weisliegend sandstones (three sites) and overlying Zechstein carbonates (two sites). Except for one site of fault zone gypsum, characteristic remanent magnetization directions were isolated for all 14 sites using alternating field and thermal step demagnetization. These directions provide a negative fold test, indicating that the remanence postdates Jurassic fault block tilting. Rock magnetic measurements show that the Kupferschiefer shale marks a redox front between the oxidized Weissliegend sandstones and non-oxidized Zechstein carbonates. The 14 site directions give a Late Jurassic paleopole at 149?±?3?Ma. It is significantly different from the paleopole reported by E.C. Jowett and others for primary or early diagenetic Rote F?ule alteration that gives an age of 254?±?6?Ma on the current apparent polar wander path and is associated with Kupferschiefer mineralization. We suggest that the Late Jurassic extensional tectonic event that formed the nearby North German Basin also reactivated Variscan basement faults and extended them up through the overlying strata, thereby allowing hydrothermal basement fluids to ascend and epigenetically mineralize the Kupferschiefer shale. The possibility of a 53?±?3?Ma mineralization age is also considered.     

Estimating groundwater residence time using multiple regression model based on fluoride dissolution: an exploration of possibilities

High levels of fluoride concentration were observed in deep groundwater of the Mizunami area in Central Japan. Fluoride occurs mainly due to the reaction between granitic basement rock and groundwater. Granites were collected, crushed to powder, and then allowed to react with purified water for 80 days. Water–rock interaction results showed that the major factor affecting fluoride concentration is the residence time of the groundwater. Coexisting ions have also some contribution toward fluoride concentration. The groundwater residence time in the Mizunami area was estimated by applying results of water–rock interaction to correspond with field data. A regression model relating fluoride concentration, residence time, and coexisting ions was developed. The parameters of the regression model were determined using the genetic algorithms technique. Residence time was estimated by extrapolating experimental data to correspond with filed data. Near the recharge area, residence times in the potential fluoride source rock varied between 1 and 2,000 years, whereas near the discharge area residence times were in excess of tens of thousands of years. The groundwater residence time was also estimated by the groundwater particle-tracking-flow model. The estimates of groundwater residence time based on geochemical regression model were often larger than estimates of groundwater residence time developed by particle-tracking analysis using a groundwater flow model. There were large uncertainties—on the order of 10–10,000 years—in the estimates based on geochemical data.     

The origin of fluoride-rich groundwater in Mizunami area, Japan — Mineralogy and geochemistry implications

The aim of this paper was to explore new factors that might be reasons for the occurrence of fluoride-rich groundwater in the area around a construction site. During the construction of two deep shafts of the Mizunami Underground Research Laboratory (MIU) in Mizunami city, central Japan, a large quantity of groundwater with high fluoride concentration was charged into the shafts. Chemical investigation carried out during the excavation revealed that fluoride concentrations in the area around the MIU site greatly exceeded those prescribed by Japanese standards. Therefore, the origin of fluoride ion was experimentally investigated. Samples were collected from the core of a deep borehole drilled in the study area. The weathering - and alteration levels of the collected granites varied greatly. Granitic powders were used to measure fluoride content in the granitic rock mass. The fluoride content ranged between 200 and 1300 mg/kg. The powders were reacted with purified water for 80 days. The results of water–rock interaction showed granitic rock to be one of the main sources of fluoride-rich groundwater in Mizunami area. Fluoride concentrations in these solutions that were shaken for 80 days varied between 2 and 7 mg/l. This change may have occurred as a result of the spatial distribution of fluoride ions in the granite mass as evidenced by mineralogical analysis of fluoride content in several specimens. X-ray powder diffraction analysis of the rock before- and after the water–rock interaction tests manifested that the presence of fluorite mineral was relatively small compared to other minerals. The degree of weathering and alteration might be an additional factor causing dissolution of fluoride-rich minerals. However, it was difficult to interpret the change in fluorite composition by X-ray diffraction analysis.     

Direct evidence for nitrogen isotope discrimination during sedimentation and early diagenesis in Lake Kasumigaura, Japan

Sediment core samples from the center of Lake Kasumigaura, Japan, were collected from 1979 to 2007 at intervals of 1 month to 5 yr. We evaluated the degree of modification in N isotope composition during sedimentation and diagenesis. We estimated the degree of isotope discrimination during diagenesis by comparing historical changes in N isotope composition of the surface sediment (top 2 cm) against the vertical profile of the isotope composition of sediment core samples (15 cm depth). The degree of ¹⁵N enrichment during sedimentation appeared to be significant under the preferential N decomposition that occurred in the periods with low C/N ratio values of suspended particulate organic matter. We documented ¹⁵N depletion in sediment deeper than approximately 3 cm during diagenesis. The contrasting directions of N isotope discrimination during sedimentation and diagenesis suggest changing mechanisms of isotopic shift across an oxidation-reduction boundary.     

Particle size effect on the saturation of methane hydrate in sediments – Constrained from experimental results

Except for those occurring at seafloor, most of natural gas hydrate form in sediments and are subject to the influence of sediment. Among these factors, the particle size effect on hydrate saturation level in sediment have been studied with a series of silica sands with various sizes, and the results obtained clearly indicate that particle size does play an important role in affecting the saturation level of hydrate in sediments. The proton relaxation times of water confined in the same series of silica sands, which were determined with NMR measurement, show logarithmic relationship with particle size. By comprehensive consideration of the results of hydrate saturation and water proton relaxation times, the particle size effect observed is tentatively explained by the water availability for hydrate formation in sediments.     

电法探查海岸带含水层咸淡水界面的调查研究

本文在理论上对电法探查多层土层组成的海岸带含水层的咸淡水界面的可能性进行探讨的基础上,对太平洋沿岸某地区进行了实地调查研究.在测量设置在海岸附近及分布于海岸纵深方向的调查井垂直方向电导率的同时,在调查井附近进行了电法探查.结果表明,电法探查的咸淡水界面的深度与依据井水电导率区分的混合区域上端几乎一致,即对于不同类别土质构成的岩土层,电法不但能探查确定咸淡水界面的深度,而且与以往的手法比较也是一种简单、快速、可靠、成本低廉的确定咸淡水界面深度的方法.     

Estimation of mean residence times of subsurface waters using seasonal variation in deuterium excess in a small headwater catchment in Japan

We measured deuterium excess (d = δD ? 8δ¹⁸O) in throughfall, groundwater, soil water, spring water, and stream water for 3 years in a small headwater catchment (Matsuzawa, 0·68 ha) in the Kiryu Experimental Watershed in Japan. The d value represents a kinetic effect produced when water evaporates. The d value of the throughfall showed a sinusoidal change (amplitude: 6·9‰ relative to Vienna standard mean ocean water (V‐SMOW)) derived from seasonal changes in the source of water vapour. The amplitude of this sinusoidal change was attenuated to 1·3–6·9‰ V‐SMOW in soil water, groundwater, spring water, and stream water. It is thought that these attenuations derive from hydrodynamic transport processes in the subsurface and mixing processes at an outflow point (stream or spring) or a well. The mean residence time (MRT) of water was estimated from d value variations using an exponential‐piston flow model and a dispersion model. MRTs for soil water were 0–5 months and were not necessarily proportional to the depth. This may imply the existence of bypass flow in the soil. Groundwater in the hillslope zone had short residence times, similar to those of the soil water. For groundwater in the saturated zone near the spring outflow point, the MRTs differed between shallow and deeper groundwater; shallow groundwater had a shorter residence time (5–8 months) than deeper groundwater (more than 9 months). The MRT of stream water (8–9 months) was between that of shallow groundwater near the spring and deeper groundwater near the spring. The seasonal variation in the d value of precipitation arises from changes in isotopic water vapour composition associated with seasonal activity of the Asian monsoon mechanism. The d value is probably an effective tracer for estimating the MRT of subsurface water not only in Japan, but also in other East Asian countries influenced by the Asian monsoon. Copyright © 2006 John Wiley & Sons, Ltd.     

The distribution of chiral asymmetry in meteorites: An investigation using asymmetric autocatalytic chiral sensors

We separated and analyzed several organic and inorganic phases of the carbonaceous chondrite matrix to determine whether they contained any inherent asymmetry. Our intent was to determine any possible foci of asymmetry besides the one determined for meteoritic amino acids. As a probe, we employed a very sensitive asymmetric autocatalytic reaction. We were able to determine that asymmetry still resides in powders after extraction with water and solvents as well as in the insoluble organic material (IOM) obtained after demineralization. Asymmetry is not found any longer in the IOM after hydrothermal treatment and in meteorite powders from which all organics had been removed by O₂ plasma at low temperature. The data are interpreted to indicate a diverse molecular asymmetry residing in yet unknown meteorite organics; these organics might have had an inductive effect on organic molecular evolution upon exogenous delivery to the early Earth.