Analysis of seawater and different highly saline natural waters by capillary zone electrophoresis

Innovative applications of capillary zone electrophoresis (CZE) to the determination of inorganic ions in environmental aquatic samples of high salinity and, particularly, in seawater are reviewed. Emphasis is placed on advanced approaches utilized for securing separation performance from being degraded by the presence of matrix salts and for simultaneous separation of ions different in natural abundance. Also covered are methodologies of present or possible use to evolve the method's practical utility to trace-level ions. Surveyed procedures are tabulated for the purpose of facilitating the method selection or further development. In addition, brief background information on basic methodological principles of CZE in inorganic ion analysis is given for a better orientation of those intending or just beginning to put CZE to work. Finally, possible future research trends and developments of CZE in the area are briefly discussed.     

A predictive model (ETLM) for As(III) adsorption and surface speciation on oxides consistent with spectroscopic data

Arsenic(III) adsorption reactions are thought to play a critical role in the mobility of arsenic in the environment. It is the nature of the As(III) surface species that must be known on a wide variety of minerals and over a range of pH, ionic strength and surface coverage in order to be able to predict adsorption behavior. EXAFS and XANES spectroscopic studies have identified bidentate, binuclear inner-sphere surface species and/or an outer-sphere species, but only a few oxides have been examined. These results need to be integrated with a predictive surface complexation model in order to ascertain the environmental conditions under which the different surface species may be important on a wide range of solids. In the present study, the surface species information from XAFS and XANES studies has been built into a recent extension of the triple-layer model (ETLM) for the formation of inner-sphere complexes of anions that takes into account the electrostatics of water dipole desorption during ligand exchange reactions. The ETLM has been applied to regress surface titration, proton coadsorption, and As(III) adsorption data over extensive ranges of pH, ionic strength, electrolyte type and surface coverage for magnetite, goethite, gibbsite, amorphous hydrous alumina, hydrous ferric oxide (HFO), ferrihydrite, and amorphous iron oxide. Two principal reactions forming inner- and outer-sphere As(III) surface species,

     

Morphological transitions for pore water and pore air during drying and wetting processes in partially saturated sand

Acta Geotechnica - Water retention characteristics are important for modeling the mechanical and hydraulic behavior of partially saturated sand. It is well known that the soil water characteristic...     

Iron–bentonite interactions in the Kawasaki bentonite deposit,Zao area,Japan

Greenish veins occurring in brecciated bentonite were found in the Kawasaki bentonite deposit of the Zao region in Miyagi Prefecture, Japan. Their occurrence possibly indicates the interaction of bentonite with Fe-rich hydrothermal solutions. In order to prove the hypothesis and understand the long-term mineralogical and petrographic evolution of bentonite during such interactions, the greenish veins and the surrounding altered bentonite were analyzed using X-ray fluorescence (XRF), scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analysis (EPMA), scanning transmission electron microscopy with energy dispersed spectroscopy (STEM-EDS) and micro X-ray absorption near-edge structure (XANES). The greenish veins resulting from hydrothermal solution are composed of mixed-layer minerals consisting of smectite and glauconite (glaucony), pyrite and opal. The occurrences indicate that glaucony and pyrite formed almost simultaneously from hydrothermal solution prior to opal precipitation. The mineral assemblages of the greenish veins and their surroundings indicate that the hydrothermal activity had most likely taken place at a temperature of less than 100 °C and that the pH and Eh conditions of the reacted solution were neutral to alkaline pH and reducing. The unaltered bentonite is composed mainly of Al smectite and opal. These minerals coexist as a mixture within the resolution level of the microprobe analyses. On the other hand, the bentonite in contact with the greenish veins consists of discrete opal grains and dioctahedral Al smectite containing Fe and was altered mineralogically and petrographically by the hydrothermal activity. Both the clay minerals and the opal were formed by dissolution and subsequent precipitation from the interaction of the original bentonite with the hydrothermal solution.     

Chemical overprinting of magmatism by weathering: A practical method for evaluating the degree of chemical weathering of granitoids

Quantitative determination of the degree of chemical weathering of rocks is a fundamental task in environmental and engineering geology, and many weathering indices based on whole-rock chemistry have been proposed. However, most classical indices are of limited application to granitoids in a wide area, because these lithotypes generally exhibit wide chemical variation arising from their petrogenesis. The chemical evolution produced during rock weathering, therefore, overprints pre-existing magmatic chemical variation. This problem can cause many classical weathering indices to yield misleading results. This study proposes a method that compensates for the influence of petrogenesis on calculation of the weathering index. The method is based on a bivariate plot of the magmatic chemical variation (MCV) in granitoids, and the degree of chemical weathering (DCW). The MCV axis must be based on an element that reflects magmatic processes and is also relatively immobile during rock weathering. In this study TiO₂ contents are utilized for the MCV. The DCW axis is fundamentally defined by the ratios of more-mobile to less-mobile elements during weathering, and hence many classical indices can be applied. The improved value of the degree of chemical weathering (DCW_i) for a weathered rock is derived by:

DCWi=s×(MCVCV-MCV₁)+DCW₁${\text{DCW}}_{\text{i}}=\text{s}\times ({\text{MCV}}_{\text{CV}}-{\text{MCV}}_1)+{\text{DCW}}_1$

where MCV₁ is the measured composition (e.g. TiO₂ content) of the weathered rock. DCW₁ denotes the ratios of more-mobile to less-mobile elements of the weathered rock. The “s” parameter is the slope of the least square linear regression for fresh granitoids in the MCV–DCW relationship. MCV_CV is a correction factor which is given by the average point on the MCV axis (e.g. average TiO₂) of the fresh rocks. This method is useful for evaluating the degree of weathering of various granitoids, and enhances the practical application of many weathering indices.     

Sr isotope excursion across the Precambrian–Cambrian boundary in the Three Gorges area, South China

The Precambrian/Cambrian (PC/C) boundary is one of the most important intervals for the evolution of life. However, the scarcity of well-preserved outcrops across the boundary leaves an obstacle in decoding surface environmental changes and patterns of biological evolution.In south China, strata through the PC/C boundary are almost continuously exposed and contain many fossils, suitable for study of environmental and biological change across the PC/C boundary. We undertook deep drilling at four sites in the Three Gorges area to obtain continuous and fresh samples without surface alteration and oxidation. ⁸⁷Sr/⁸⁶Sr ratios of the fresh carbonate rocks, selected based on microscopic observation and geochemical signatures of Mn/Sr and Rb/Sr ratios, aluminum and silica contents, and δ¹³C and δ¹⁸O values, were measured with multiple collector-inductively coupled plasma–mass spectrometric techniques.The chemostratigraphy of ⁸⁷Sr/⁸⁶Sr ratios of the drilled samples displays a smooth curve and a large positive anomaly just below the PC/C boundary between the upper part of Baimatuo Member of the Dengying Formation and the lower part of the Yanjiahe Formation. The combination of chemostratigraphies of δ¹³C and ⁸⁷Sr/⁸⁶Sr indicates that the ⁸⁷Sr/⁸⁶Sr excursions preceded the δ¹³C negative excursion, and suggests that global regression or formation of the Gondwana supercontinent, possibly together with a high atmospheric pCO₂, caused biological depression.     

The period–luminosity relation for type II Cepheids in globular clusters

We report the result of our near-infrared observations ( JHK _s) for type II Cepheids (including possible RV Tau stars) in galactic globular clusters. We detected variations of 46 variables in 26 clusters (10 new discoveries in seven clusters) and present their light curves. Their periods range from 1.2 d to over 80 d. They show a well-defined period–luminosity relation at each wavelength. Two type II Cepheids in NGC 6441 also obey the relation if we assume the horizontal branch stars in NGC 6441 are as bright as those in metal-poor globular clusters in spite of the high metallicity of the cluster. This result supports the high luminosity which has been suggested for the RR Lyr variables in this cluster. The period–luminosity relation can be reproduced using the pulsation equation     assuming that all the stars have the same mass. Cluster RR Lyr variables were found to lie on an extrapolation of the period–luminosity relation. These results provide important constraints on the parameters of the variable stars.
Using Two Micron All-Sky Survey (2MASS) data, we show that the type II Cepheids in the Large Magellanic Cloud (LMC) fit our period–luminosity relation within the expected scatter at the shorter periods. However, at long periods (   P > 40  d, i.e. in the RV Tau star range) the LMC field variables are brighter by about one magnitude than those of similar periods in galactic globular clusters. The long-period cluster stars also differ from both these LMC stars and galactic field RV Tau stars in a colour–colour diagram. The reasons for these differences are discussed.