A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process

Eight DSDP/ODP cores were analyzed for major ion concentrations and δ³⁷Cl values of water-soluble chloride (δ³⁷Cl_WSC) and structurally bound chloride (δ³⁷Cl_SBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (X_WSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (X_SBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl⁻ site and the water-soluble Cl⁻ site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ³⁷Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ³⁷Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ³⁷Cl values also have variable Cl⁻ / SO₄² ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ³⁷Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ³⁷Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of ³⁷Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ³⁷Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ³⁷Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Increasing critical sensitivity of the Load/Unload Response Ratio before large earthquakes with identified stress accumulation pattern

The Load/Unload Response Ratio (LURR) method is proposed for short-to-intermediate-term earthquake prediction [Yin, X.C., Chen, X.Z., Song, Z.P., Yin, C., 1995. A New Approach to Earthquake Prediction — The Load/Unload Response Ratio (LURR) Theory, Pure Appl. Geophys., 145, 701–715]. This method is based on measuring the ratio between Benioff strains released during the time periods of loading and unloading, corresponding to the Coulomb Failure Stress change induced by Earth tides on optimally oriented faults. According to the method, the LURR time series usually climb to an anomalously high peak prior to occurrence of a large earthquake. Previous studies have indicated that the size of critical seismogenic region selected for LURR measurements has great influence on the evaluation of LURR. In this study, we replace the circular region usually adopted in LURR practice with an area within which the tectonic stress change would mostly affect the Coulomb stress on a potential seismogenic fault of a future event. The Coulomb stress change before a hypothetical earthquake is calculated based on a simple back-slip dislocation model of the event. This new algorithm, by combining the LURR method with our choice of identified area with increased Coulomb stress, is devised to improve the sensitivity of LURR to measure criticality of stress accumulation before a large earthquake. Retrospective tests of this algorithm on four large earthquakes occurred in California over the last two decades show remarkable enhancement of the LURR precursory anomalies. For some strong events of lesser magnitudes occurred in the same neighborhoods and during the same time periods, significant anomalies are found if circular areas are used, and are not found if increased Coulomb stress areas are used for LURR data selection. The unique feature of this algorithm may provide stronger constraints on forecasts of the size and location of future large events.     

Geologic correlation between the Neoproterozoic Sergipano belt (NE Brazil) and the Yaoundé belt (Cameroon, Africa)

The Yaoundé belt (Cameroon) and the Sergipano belt (NE Brazil) belonged to a major and continuous Neoproterozoic orogen at the northern margin of the ancient Congo-São Francisco craton. The Yaoundé belt comprises schists, quartzites, gneisses and migmatitic gneisses grouped into three domains; the low-grade Mbalmayo Group in south and the medium- to high-grade Yaoundé and Bafia Group in north. The Sergipano belt is divided into six domains, the three southernmost of which are mostly made up of clastic and chemical metasedimentary rocks whereas the others are more diverse with a migmatite–gneiss complex, and two metavolcanicplutonic complexes. In general, the two belts show structural vergence and decrease of metamorphic grade towards the craton; three main deformation phases are recognized in the Sergipano belt in contrast with two described in the Yaoundé belt. The minimum age of Pan-African-Brasiliano collision in the Sergipano belt is constrained at 628 ± 12 Ma on syn-collision granites, whereas in the Yaoundé belt collision took place between 620 and 610 Ma, i.e. the age of granulite facies metamorphism. Sm–Nd isotope geochemistry and U–Pb age dating indicate that most clastic metasedimentary rocks in both belts were derived from sources to the north and, to a lesser degree, from the cratons to the south.     

HP–LT Variscan metamorphism in the Cubito-Moura schists (Ossa-Morena Zone, southern Iberia)

Multi-equilibrium thermobarometry shows that low-grade metapelites (Cubito-Moura schists) from the Ossa–Morena Zone underwent HP–LT metamorphism from 340–370 °C at 1.0–0.9 GPa to 400–450 °C at 0.8–0.7 GPa. These HP–LT equilibriums were reached by parageneses including white K mica, chlorite and chloritoid, which define the earliest schistosity (S₁) in these rocks. The main foliation in the schists is a crenulation cleavage (S₂), which developed during decompression from 0.8–0.7 to 0.4–0.3 GPa at increasing temperatures from 400–450 °C to 440–465 °C. Fe³⁺ in chlorite decreased greatly during prograde metamorphism from molar fractions of 0.4 determined in syn-S₁ chlorites down to 0.1 in syn-S₂ chlorites. These new data add to previous findings of eclogites in the Moura schists indicating that a pile of allochtonous rocks situated next to the Beja-Acebuches oceanic amphibolites underwent HP–LT metamorphism during the Variscan orogeny. To cite this article: G. Booth-Rea et al., C. R. Geoscience 338 (2006).     

Hydrogen isotope of individual n-alkanes from modern sediments and their application to environments

Hydrogen isotopes are commonly fractionated to a much greater extent and as a result display larger variations in δ values, In terms of the hydrogen isotope ratios of individual n-alkanes of 16 samples of modern sediments selected from four different locations in the southern part of Gansu, China, the δD values for most of the n-alkanes varied from -150‰-300‰, Variations in δD also occurred between different ranges of n-alkanes, effects of environmental changes on the hydrogen isotopic compositions of individual n-alkanes have been detected. Besides the δD values of n-alkanes, the δD values of lipids including pristane （Pr）, phytane （Ph） were also examined, by the combination of D/H ratios with molecular fingerprinting, Our results further support the notion that hydrogen isotopes of n-alkanes from modern sediments can act as paleoclimatic and paleoenvironmental proxies and provide invaluable new sources of information in the research of paleoenvironment reconstruction.     

On the Importance of Geolithological Features for the Estimate of the Site Response: The Case of Catania Metropolitan Area (Italy)

The evaluation of seismic site response in the urban area of Catania was tackled by selecting test areas having peculiar lithological and structural features, potentially favourable to large local amplifications of ground motion. The two selected areas are located in the historical downtown and in the northern part of Catania where the presence of a fault is evident. Site response was evaluated using spectral ratio technique taking the horizontal- to-vertical component ratio of ambient noise. Inferences from microtremor measurements are compared with results from synthetic accelerograms and response spectra computed at all drillings available for this area. Such method is particularly suitable in urban areas where the nature of the outcropping geological units is masked by city growth and anthropic intervention on the surface geology. The microtremor H/V spectral ratios evaluated at soft sites located within the downtown profile tend to be smaller than that usually reported in the literature for such soils. A tendency for amplifications to peaks near 2 Hz is observed only in some sites located on recent alluvial deposits. Evidences for amplifications of site effects (frequency range 4–8 Hz) were observed in the sampling sites located on the fault, with a rapid decrease of spectral amplitude just a few tenths of metres away from the discontinuity. Numerical simulations evidenced the importance of geolithological features at depth levels even greater than 20–30 m. Besides this, the results strongly confirm the importance of the subsurface geological conditions, in the estimate of seismic hazard at urban scale.     

Assessing the Vibrational Frequencies of the Cathedral of Cologne (Germany) by Means of Ambient Seismic Noise Analysis

Ambient seismic noise measurements were conducted inside the Cathedral of Cologne (Germany) for assessing its frequencies of vibration and for checking whether these occur in the range where soil amplification is expected. If this is the case, damages may increase in case of an earthquake due to an increased structural response of the building. Analysis of the ratio between the horizontal and vertical components of the spectra recorded at stations located inside the building as well as the ratio between the corresponding components of the spectra recorded simultaneously inside the building and at a reference station placed in the basement of the cathedral indicated several modes of vibration. Facilitated by these results an assessment of the seismic vulnerability was attempted for a 2D ground motion scenario using the finite element method.     

Use of electrical resistivity methods for detecting subsurface fresh and saline water and delineating their interfacial configuration: a case study of the eastern Dead Sea coastal aquifers, Jordan

The alluvial aquifer is the primary source of groundwater along the eastern Dead Sea shoreline, Jordan. Over the last 20 years, salinity has risen in some existing wells and several new wells have encountered brackish water in areas thought to contain fresh water. A good linear correlation exists between the water resistivity and the chloride concentration of groundwater and shows that the salinity is the most important factor controlling resistivity. Two-dimensional electrical tomography (ET) integrated with geoelectrical soundings were employed to delineate different water-bearing formations and the configuration of the interface between them. The present hydrological system and the related brines and interfaces are controlled by the Dead Sea base level, presently at 410 m b.s.l. Resistivity measurements show a dominant trend of decreasing resistivity (thus increasing salinity) with depth and westward towards the Dead Sea. Accordingly, three zones with different resistivity values were detected, corresponding to three different water-bearing formations: (1) strata saturated with fresh to slightly brackish groundwater; (2) a transition zone of brine mixed with fresh to brackish groundwater; (3) a water-bearing formation containing Dead Sea brine. In addition, a low resistivity unit containing brine was detected above the 1955 Dead Sea base level, which was interpreted as having remained unflushed by infiltrating rain.     

New data on Sr-and C-isotopic chemostratigraphy of the Upper Riphean type section (Southern Urals)

New data on Sr-and C-isotopic systematics of carbonate rocks from the Upper Riphean stratotype (Karatau Group of the southern Urals) are obtained for several southwestern sections of the Bashkirian meganticlinorium, which have not been studied before. The results obtained supplement the Sr-and C-isotopic information for the group upper horizons thus detailing chemostratigraphic characterization of the entire succession. Limestone and dolostone samples used to analyze the Sr isotope composition satisfy strict geochemical criteria of the isotopic system retentivity and have been subjected to preliminary treatment in ammonium acetate to remove secondary carbonate phases. Data on 255 samples of carbonate rocks (171 studied for the first time) show that δ¹³C value varies in the Karatau Group succession from ?2.8 to +5.9 ‰ V-PDB with several in-phase excursions from the general trend in all the sections studied in the area 90 × 130 km. The δ¹³C variation trend demarcates several levels in the carbonate succession of the Karatau Group suitable for objectives of regional stratigraphy and for C-isotope chemostratigraphic subdivision of the Upper Riphean. The results of Sr isotopic analysis of 121 samples (51 unstudied before) from the Karatau Group imply that rocks in its lower part (the Katav Formation and basal horizon of the Inzer Formation) experienced considerable secondary alterations, while limestones and dolostones of the overlying interval of the group are frequently unaltered. In the “best” samples satisfying geochemical criteria of the isotopic system retentivity, the ⁸⁷Sr/⁸⁶Sr initial ratio increases from 0.70521–0.70532 in the lower Inzer deposits to 0.70611 in the upper Min’yar carbonates, decreasing to <0.70600 near the top of the latter. Above the regional hiatus separating the Min’yar and Uk formation, this ratio grows from 0.70533 to 0.70605–0.70609 in the limestone succession of the last formation.