Fractionation mechanism of stable isotope in evaporating water body

Under Rayleigh equilibrium condition, stable isotopic ratio in residual water increases with the decrease of the residual water proportion f exponentially, and the fractionation rate of stable isotopes is inversely proportional to temperature. However, under kinetic evaporation condition, the fractionation of stable isotopes is not only related to the phase temperature but also influenced by the atmospheric humidity and the mass exchange between liquid and vapor phases. The ratio δ in residual water will not change with f after undergoing evaporation of a long time for great relative humidity. The rate that the evaporating water body reaches isotopic steady state is mainly dependent on the relative humidity in atmosphere. The analysis shows that the actual mean linear variety rates, about -30.0, of the δ18O in residual water versus the residual water proportion at Nagqu and Amdo stations are consistent with the simulated process under temperature of 20 oC and relative humidity of 50%. The distillation line simulated under Rayleigh equilibrium condition is analogous to the global meteoric water line (MWL) as the temperature is about 20 oC. Under non-equilibrium condition, the slope and constant values of distillation line are directly proportional to temperature and relative humidity. According to the basic data, the simulated distillation line is very consistent with the actual distillation line of Qinghai Lake.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

Chemical Profiles across a Jurassic Stratiform Manganese Deposit at Katsuyama in the Mino Terrane of Central Japan: Implications for Depositional Environment, Diagenetic Metal Redistribution and Paleoceanography

Abstract. Inorganic chemical compositions are determined for a series of rocks crossing an Early Jurassic stratiform manganese ore deposit in a chert‐dominant sequence at Katsuyama, in the Mino Terrane of central Japan. The lithology in the vicinity of the manganese ore bed is classified into lower bedded chert, black shale, massive chert, manganese ore and upper bedded chert, in ascending order. The rocks surrounding the manganese deposit are anomalously high in certain elements: Pb (max. 29 ppm), Ni (1140) and Co (336) in the lower bedded chert, Mo (438), As (149), Tl (29) and U (12) in the black shales, V (210) and Cr (87) in the massive chert, and MnO and W (24) in the manganese ore. The aluminum‐normalized profiles reveal a distinct zonation of redox‐sensitive elements: Pb‐Zn, Ni‐Co‐Cu(‐Zn) and U‐Cr in the lower bedded chert, Mo‐As‐Tl in the black shale, V(‐Cr) in the massive chert, and Mn‐Fe‐Ba‐W in the manganese ore, in ascending order. The lower and upper bedded cherts and manganese ore generally exhibit flat rare earth element patterns with positive Ce anomalies, whereas the uppermost part of the lower bedded chert, the black shale and massive chert have flat patterns with weak or nonexistent negative Ce anomalies and weak positive Eu anomalies. The strong enrichment in Ni, Co, W, Tl and As detected in the Katsuyama section is not recognized in other sediments, including those of anoxic deposition origin, but is identified in modern ferromanganese nodules, suggesting that metal enrichment in the Katsuyama section is essentially due to the formation of ferromanganese nodules rather than to deposition in an anoxic environment. The observed elemental zonation is well explained by equilibrium calculations, reflecting early diagenetic formation and associated gradual reduction with depth. The concentration profiles in combination with litho‐ and biostratigraphical features suggest that formation of these bedded manganese deposits was triggered by an influx of warm, saline and oxic water into a stagnant deep ocean floor basin in Panthalassa at the end of the middle Early Jurassic. Paleoceanographic environmental controls thus appear to be important factors in the formation and preservation of this type of stratiform manganese deposit.     

A statistical procedure for the analysis of seismotectonically induced hydrochemical signals: A case study from the Eastern Carpathians, Romania

Changes in the stress field of an aquifer system induced by seismotectonic activity may change the mixing ratio of groundwaters with different compositions in a well, leading to hydrochemical signals which in principle could be related to discrete earthquake events. Due to the complexity of the interactions and the multitude of involved factors the identification of such relationships is a difficult task. In this study we present an empiric statistical approach suitable to analyse if there is an interdependency between changes in the chemical composition of monitoring wells and the regional seismotectonic activity of a considered area. To allow a rigorous comparison with hydrochemistry the regional earthquake time series was aggregated into an univariate time series. This was realized by expressing each earthquake in form of a parameter “e”, taking into consideration both energetic (magnitude of a seismic event) and spatial parameters (position of epi/hypocentrum relative to the monitoring site). The earthquake and the hydrochemical time-series were synchronised aggregating the e-parameters into “earthquake activity” functions E, which takes into account the time of sampling relative to the earthquakes which occurred in the considered area. For the definition of the aggregation functions a variety of different “e” parameters were considered. The set of earthquake functions E was grouped by means of factor analysis to select a limited number of significant and representative earthquake functions E to be used further on in the relation analysis with the multivariate hydrochemical data set. From the hydrochemical data a restricted number of hydrochemical factors were extracted. Factor scores allow to represent and analyse the variation of the hydrochemical factors as a function of time. Finally, regression analysis was used to detect those hydrochemical factors which significantly correlate with the aggregated earthquake functions.This methodological approach was tested with a hydrochemical data set collected from a deep well monitored for two years in the seismically active Vrancea region, Romania. Three of the hydrochemical factors were found to correlate significantly with the considered earthquake activities. A screening with different time combinations revealed that correlations are strongest when the cumulative seismicity over several weeks was considered. The case study also showed that the character of the interdependency depends sometimes on the geometrical distribution of the earthquake foci. By using aggregated earthquake information it was possible to detect interrelationships which couldn't have been identified by analysing only relations between single geochemical signals and single earthquake events. Further on, the approach allows to determine the influence of different seismotectonic patterns on the hydrochemical composition of the sampled well. The method is suitable to be used as a decision instrument in assessing if a monitoring site is suitable or not to be included in a monitoring net within a complex earthquake prediction strategy.     

Identifying sources of groundwater recharge in the Merguellil basin (Tunisia) using isotopic methods: implication of dam reservoir water accounting

Thirty-two groundwater samples collected from the Merguellil Wadi basin (central Tunisia) complemented by the Haouareb dam reservoir water samples have been isotopically analysed in order to investigate the implication of the reservoir water to recharging the aquifer, and also to infer the sources, relative ages and mixing processes in the aquifer system. Plots of the stable isotopes data against the local meteoric lines of Tunis-Carthage and Sfax indicate a strong implication of the dam water noticeable up to a distance of 6–7 km. A contribution as much as 80% of the pumped water has been evidenced using isotopic mass balance. In addition, poorly distinguished water clusters in the stable isotope plots, but clearly identified in the diagrams δ¹⁸O versus ³H and ³H versus ¹⁴C, indicate various water types related to sources and timing of recharge. The isotopic signatures of the dam accounting water, the “old” and “native” recharged waters, have been evidenced in relation to their geographical distribution and also to their radiogenic isotopes (³H and ¹⁴C) contents. In the south-western part of the aquifer, mixing process occurs between the dam reservoir water and both the “old” and “native” water components.     

Hydrography of the eastern Arabian Sea during summer monsoon 2002

Hydrographic observations in the eastern Arabian Sea (EAS) during summer monsoon 2002 (during the first phase of the Arabian Sea Monsoon Experiment (ARMEX)) include two approximately fortnight-long CTD time series. A barrier layer was observed occasionally during the two time series. These ephemeral barrier layers were caused byin situ rainfall, and by advection of low-salinity (high-salinity) waters at the surface (below the surface mixed layer). These barrier layers were advected away from the source region by the West India Coastal Current and had no discernible effect on the sea surface temperature. The three high-salinity water masses, the Arabian Sea High Salinity Water (ASHSW), Persian Gulf Water (PGW), and Red Sea Water (RSW), and the Arabian Sea Salinity Minimum also exhibited intermittency: they appeared and disappeared during the time series. The concentration of the ASHSW, PGW, and RSW decreased equatorward, and that of the RSW also decreased offshore. The observations suggest that the RSW is advected equatorward along the continental slope off the Indian west coast.     

Geochemistry of Late Cretaceous （ 60 - 67 Ma） igneous activities in the Hebrides Terrace seamount （guyot） area, Scotland

Tholeiitic basalts in various stages of alteration were dredged from Late Cretaceous volcanic rocks (60 -67 Ma) in the Hebrides Terrace seamount area in the Atlantic Ocean. These rocks are extrusive olivine basalts, including high- and low-Al basalts. High-Al basalts are depleted in MgO, CaO, Cr,Sc, V, St, Zr and enriched in TiO2, Na2O, Nb, Rb as compared with low-A1 basalts. Petrography and bulk-rock composition (major, trace and rare-earth elements) data defined clear tholeiitic suites displaying possible liquid lines of descent related to different degrees of crystal fractionation and partial melting.Isotopic dating of dredged samples gave the guyot an age of 60 - 67 Ma, in support of the assumption that it was formed during the Late Cretaceous.