Effects of humic substances on Fe(II) sorption onto aluminum oxide and clay

We studied the effects of humic substances (HS) on the sorption of Fe(II) onto Al-oxide and clay sorbents at pH 7.5 with a combination of batch kinetic experiments and synchrotron Fe K-edge EXAFS analyses. Fe(II) sorption was monitored over the course of 4 months in anoxic clay and Al-oxide suspensions amended with variable HS types (humic acid, HA; or fulvic acid, FA) and levels (0, 1, and 4 wt%), and with differing Fe(II) and HS addition sequences (co-sorption and pre-coated experiments, where Fe(II) sorbate was added alongside and after HS addition, respectively). In the Al-oxide suspensions, the presence of HS slowed down the kinetics of Fe(II) sorption, but had limited, if any, effect on the equilibrium aqueous Fe(II) concentrations. EXAFS analyses revealed precipitation of Fe(II)–Al(III)-layered double hydroxide (LDH) phases as the main mode of Fe(II) sorption in both the HA-containing and HA-free systems. These results demonstrate that HS slow down Fe(II) precipitation in the Al-oxide suspensions, but do not affect the composition or stability of the secondary Fe(II)–Al(III)-LDH phases formed. Interference of HS with the precipitation of Fe(II)–Al(III)-LDH was attributed to the formation organo-Al complexes HS limiting the availability of Al for incorporation into secondary layered Fe(II)-hydroxides. In the clay systems, the presence of HA caused a change in the main Fe(II) sorption product from Fe(II)–Al(III)-LDH to a Fe(II)-phyllosilicate containing little structural Al. This was attributed to complexation of Al by HA, in combination with the presence of dissolved Si in the clay suspension enabling phyllosilicate precipitation. The change in Fe(II) precipitation mechanism did not affect the rate of Fe(II) sorption at the lower HA level, suggesting that the inhibition of Fe(II)–Al(III)-LDH formation in this system was countered by enhanced Fe(II)-phyllosilicate precipitation. Reduced rates of Fe(II) sorption at the higher HA level were attributed to surface masking or poisoning by HA of secondary Fe(II) mineral growth at or near the clay surface. Our results suggest that HS play an important role in controlling the kinetics and products of Fe(II) precipitation in reducing soils, with effects modulated by soil mineralogy, HS content, and HS properties. Further work is needed to assess the importance of layered Fe(II) hydroxides in natural reducing environments.     

Biostratigraphy and floristic evolution of coal swamp floras of a part of Talcher Basin,India: a window on a Permian temperate ecosystem

The present megafloral assemblage recorded from the Barakar sediments of Dholpahar section along Singda rivulet near Gopal Prasad Village in Talcher Basin comprises of equisetaceous stems, Gangamopteris buriadica, Palaeovittaria kurzii and 19 species of the genus Glossopteris. Record of Gangamopteris, Palaeovittaria and many narrow mesh forms of Glosspteris viz., G. angustifolia, G. churiensis, G. communis, G. recurva, G. spatulata, G. stenoneura, G. tenuifolia, G. vulgaris and G. zeilleri from two older fossiliferous horizons demonstrates that these fossils were preserved during Lower Barakar sedimentation. The report of middle and broad mesh forms of Glossopteris viz., G. barakarensis, G. browniana, G. indica, G. intermittens, G. karharbariensis, G. nakkarea, G. oldhamii, G. taeniensis and G. retifera in the youngest fossiliferous horizons reveals that these fossils were preserved during the deposition of Upper Barakar sediments. The continuation of some of the Karharbari plant fossils in the early phase of Barakar Formation and their disappearance in the flora of Late Barakar suggests a shift in the climatic setup. Palaeoclimate and palaeovegetation of this area are also summarised in this study. Moreover, the fossil assemblages of different fossiliferous beds of Dholpahar section demonstrate the evolution of midrib and meshes in different reticulate leaves.     

The pressure–temperature–time path of migmatites from the Sikkim Himalaya

A combined metamorphic and isotopic study of lit‐par‐lit migmatites exposed in the hanging wall of the Main Central Thrust (MCT) from Sikkim has provided a unique insight into the pressure–temperature–time path of the High Himalayan Crystalline Series of the eastern Himalaya. The petrology and geochemistry of one such migmatite indicates that the leucosome comprises a crystallized peraluminous granite coexisting with sillimanite and alkali feldspar. Large garnet crystals (2–3 mm across) are strongly zoned and grew initially within the kyanite stability field. The melanosome is a biotite–garnet pelitic gneiss, with fibrolitic sillimanite resulting from polymorphic inversion of kyanite. By combining garnet zoning profiles with the NaCaMnKFMASHTO pseudosection appropriate to the bulk composition of a migmatite retrieved from c. 1 km above the thrust zone, it has been established that early garnet formed at pressures of 10–12 kbar, and that subsequent decompression caused the rock to enter the melt field at c. 8 kbar and c. 750 °C, generating peritectic sillimanite and alkali feldspar by the incongruent melting of muscovite. Continuing exhumation resulted in resorption of garnet. Sm–Nd growth ages of garnet cores and rim, indicate pre‐decompression garnet growth at 23 ± 3 Ma and near‐peak temperatures during melting at 16 ± 2 Ma. This provides a decompression rate of 2 ± 1 mm yr^?1 that is consistent with exhumation rates inferred from mineral cooling ages from the eastern Himalaya. Simple 1D thermal modelling confirms that exhumation at this rate would result in a near‐isothermal decompression path, a result that is supported by the phase relations in both the melanosome and leucosome components of the migmatite. Results from this study suggest that anatexis of Miocene granite protoliths from the Himalaya was a consequence of rapid decompression, probably in response to movement on the MCT and on the South Tibetan detachment to the north.     

Utilization of high-resolution EGM2008 gravity data for geological exploration over the Singhbhum-Orissa Craton,India

High-resolution EIGEN6C4 and EGM2008 Bouguer gravity data of 2190 degree spherical harmonic over the Singhbhum-Orissa Craton, India, have been generated from the International Centre for Global Earth Models. The Bouguer gravity anomaly difference maps of (i) in situ and EIGEN6C4, (ii) in situ and EGM2008 and iii) EIGEN6C4 and EGM2008 of the study area are compared. It reveals that EIGEN6C4 has lesser systematic error than EGM2008. However, from different profile plots of Bouguer gravity, east–west horizontal derivative and north–south horizontal derivative anomalies of the in situ, EIGEN6C4 and EGM2008, it is observed that most of the signatures of lithounits and geological structural elements are delineated very well by EGM2008 and match 94–98% with those of EIGEN6C4. Further, the Bouguer gravity, east–west horizontal derivative and north–south horizontal derivative anomalies of EGM2008 data over the study area have been used effectively for identifying various lithounits and geological structural elements.     

Determination of rare earth and refractory trace element abundances in early solar system objects by ion microprobe

Experimental and analytical procedures devised for measurement of rare earth element (REE) abundances using a secondary ion mass spectrometer (ion microprobe) are described. This approach is more versatile than the conventional techniques such as neutron activation analysis and isotope dilution mass spectrometry by virtue of its high spatial resolution that allows determination of REE abundances in small domains (10-20 micron) within individual mineral phases. The ion microprobe measurements are performed at a low mass-resolving power adopting the energy-filtering technique (Zinner and Crozaz 1986) for removal and suppression of unresolved complex molecular interferences in the REE masses of interest. Synthetic standards are used for determining various instrument specific parameters needed in the data deconvolution procedure adopted for obtaining REE abundances. Results obtained from analysis of standards show that our ion microprobe may be used for determining REE abundances down to ppm range with uncertainties of ∼ 10 to 15%. Abundances of rare earth and several other refractory trace elements in a set of early solar system objects isolated from two primitive carbonaceous chondrites were determined using the procedures devised by us. The results suggest that some of these objects could be high temperature nebular condensates, while others are products of melting and recrystallization of precursor nebular solids in a high temperature environment.