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.     

3D and 4D controls on carbonate depositional systems: sedimentological and sequence stratigraphic analysis of an attached carbonate platform and atoll (Miocene, Níjar Basin, SE Spain)

This study investigates the controls on three-dimensional stratigraphic geometries and facies of shallow-water carbonate depositional sequences. A 15 km² area of well-exposed Mid to Late Miocene carbonates on the margin of the Níjar Basin of SE Spain was mapped in detail. An attached carbonate platform and atoll developed from a steeply sloping basin margin over a basal topographic unconformity and an offshore dacite dome (Late Miocene). The older strata comprise prograding bioclastic (mollusc and coralline algae) dominated sediments and later Messinian Porites reefs form prograding and downstepping geometries (falling stage systems tract). Seven depositional sequences, their systems tracts and facies have been mapped and dated (using Sr isotopes) to define their morphology, stratigraphic geometries, and palaeo-environments. A relative sea-level curve and isochore maps were constructed for the three Messinian depositional sequences that precede the late Messinian evaporative drawdown of the Mediterranean. The main 3D controls on these depositional sequences are interpreted as being: (i) local, tectonically driven relative sea-level changes; (ii) the morphology of the underlying sequence boundary; (iii) the type of carbonate producers [bioclastic coralline algal and mollusc-dominated sequences accumulated in lows and on slopes of < 14° whereas the Porites reef-dominated sequence accumulated on steep slopes (up to 25°) and shallow-water highs]. Further controls were: (iv) the inherited palaeo-valleys and point-sourced clastics; (v) the amount of clastic sediments; and (vi) erosion during the following sequence boundary development. The stratigraphy is compared with that of adjacent Miocene basins in the western Mediterranean to differentiate local (tectonics, clastic supply, erosion history, carbonate-producing communities) versus regional (climatic, tectonic, palaeogeographic, sea-level) controls.     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

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.     

Directional dependence of P- and S-wave propagation and polarization in foliated rocks from the Kola superdeep well: Evidence from laboratory measurements and calculations based on TOF neutron diffraction

We have measured P- and S-wave velocities on two amphibolite and two gneiss samples from the Kola superdeep borehole as a function of pressure (up to 600 MPa) and temperature (up to 600 °C). The velocity measurements include compressional (Vp) and shear wave velocities (Vs1, Vs2) propagating in three orthogonal directions which were in general not parallel to inherent rock symmetry axes or planes. The measurements are accompanied by 3D-velocities calculations based on lattice preferred orientation (LPO) obtained by TOF (Time Of Flight) neutron diffraction analysis which allows the investigation of bulk volumes up to several cubic centimetres due to the high penetration depth of neutrons. The LPO-based numerical velocity calculations give important information on the different contribution of the various rock-forming minerals to bulk elastic anisotropy and on the relations of seismic anisotropy, shear wave splitting, and shear wave polarization to the structural reference frame (foliation and lineation). Comparison with measured velocities obtained for the three propagation directions that were not in accordance with the structural frame of the rocks (foliation and lineation) demonstrate that for shear waves propagating through anisotropic rocks the vibration directions are as important as the propagation directions. The study demonstrates that proper measurement of shear wave splitting by means of two orthogonal polarized sending and receiving shear wave transducers is only possible when their propagation and polarization directions are parallel and normal to foliation and lineation, respectively.     

Did Paleogene North Atlantic rift-related eruptions drive early Eocene climate cooling?

The delivery of volcanogenic sulphur into the upper atmosphere by explosive eruptions is known to cause significant temporary climate cooling. Therefore, phreatomagmatic and phreatoplinian eruptions occurring during the final rifting stages of active flood basalt provinces provide a potent mechanism for triggering climate change.

During the early Eocene, the northeast Atlantic margin was subjected to repeated ashfall for 0.5 m.y. This was the result of extensive phreatomagmatic activity along 3000 km of the opening northeast Atlantic rift. These widespread, predominantly basaltic ashes are now preserved in marine sediments of the Balder Formation and its equivalents, and occur over an area extending from the Faroe Islands to Denmark and southern England. These ash-bearing sediments also contain pollen and spore floras derived from low diversity forests that grew in cooler, drier climates than were experienced either before or after these highly explosive eruptions. In addition, coeval plant macrofossil evidence from the Bighorn Basin, Wyoming, USA, also shows a comparable pattern of vegetation change. The coincidence of the ashes and cooler climate pollen and spore floras in northwest Europe identifies volcanism as the primary cause of climate cooling. Estimates show that whilst relatively few phreatomagmatic eruptive centres along the 3000 km opening rift system could readily generate 0.5–1 °C cooling, on an annual basis, only persistent or repeated volcanic phases would have been able to achieve the long-term cooling effect observed in the floral record. We propose that the cumulative effect of repeated Balder Formation eruptions initiated a biodiversity crisis in the northeast Atlantic margin forests. Only the decline of this persistent volcanic activity, and the subsequent climatic warming at the start of the Eocene Thermal Maximum allowed the growth of subtropical forests to develop across the region.     

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.