FT-IR Spectroscopic Investigation of Hydrous Components in Sillimanite from Eastern Ghat Granulite Belt, India

FT-IR spectra of sillimanite samples from high grade regionally metamorphosed rocks belonging to the granulite terrain (amphibolite to pyroxene granulite facies) deciphers prominent OH features. Heating experiments indicate growth of prominent band at 3161cm⁻¹. Heating above 1000°C all OH features disappear in intensity into broad features with slight shift of bands towards lower energies. Complete dehydration requires temperatures above 1000°C. Coexistence of boron and OH features are also observed in all sillimanite samples. The high temperature behaviour of sillimanite from the granulite terrain discerns that the hydrous species in sillimanite were incorporated much below 700°C, however, secondary hydration due to pegmatite activity, retrograde metamorphism and migmatisation is not ruled out. Thus a near anhydrous condition were probably not achieved during the granulite facies metamorphism in Eastern ghat granulite terrain.     

The effect of geometry and tidal forcing on hydrodynamics and net sediment transport in semi-enclosed tidal basins

A new depth-averaged exploratory model has been developed to investigate the hydrodynamics and the tidally averaged sediment transport in a semi-enclosed tidal basin. This model comprises the two-dimensional (2DH) dynamics in a tidal basin that consists of a channel of arbitrary length, flanked by tidal flats, in which the water motion is being driven by an asymmetric tidal forcing at the seaward side. The equations are discretized in space by means of the finite element method and solved in the frequency domain. In this study, the lateral variations of the tidal asymmetry and the tidally averaged sediment transport are analyzed, as well as their sensitivity to changes in basin geometry and external overtides. The Coriolis force is taken into account. It is found that the length of the tidal basin and, to a lesser extent, the tidal flat area and the convergence length determine the behaviour of the tidally averaged velocity and the overtides and consequently control the strength and the direction of the tidally averaged sediment transport. Furthermore, the externally prescribed overtides can have a major influence on tidal asymmetry in the basin, depending on their amplitude and phase. Finally, for sufficiently wide tidal basins, the Coriolis force generates significant lateral dynamics.     

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies.Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.     

Contents to Volume 8

Volume Contents

Contents to Volume 8     

Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

Temporal evolution and compositional signatures of two supervolcanic systems recorded in zircons from Mangakino volcanic centre,New Zealand

Mangakino, the oldest rhyolitic caldera centre delineated in the Taupo Volcanic Zone of New Zealand, generated two very large (super-sized) ignimbrite eruptions, the 1.21 ± 0.04 Ma >500 km³ Ongatiti and ~1.0 Ma ~1,200 km³ Kidnappers events, the latter of which was followed after a short period of erosion by the ~200 km³ Rocky Hill eruption. We present U/Pb ages and trace-element analyses on zircons from pumice clasts from these three eruptions by Secondary Ion Mass Spectrometry (SIMS) using SHRIMP-RG instruments to illustrate the evolution of the respective magmatic systems. U–Pb age spectra from the Ongatiti imply growth of the magmatic system over ~250 kyr, with a peak of crystallisation around 1.32 Ma, ~100 kyr prior to eruption. The zircons are inferred to have then remained stable in a mush with little crystallisation and/or dissolution before later rejuvenation of the system at the lead-in to eruption. The paired Kidnappers and Rocky Hill eruptions have U–Pb zircon ages and geochemical signatures that suggest they were products of a common system grown over ~200 kyr. The Kidnappers and Rocky Hill samples show similar weakly bimodal age spectra, with peaks at 1.1 and 1.0 Ma, suggesting that an inherited antecrystic population was augmented by crystals grown at ages within uncertainty of the eruption age. In the Kidnappers, this younger age peak is dominantly seen in needle-shaped low U grains with aspect ratios of up to 18. In all three deposits, zircon cores show larger ranges and higher absolute concentrations of trace elements than zircon rims, consistent with zircon crystallisation from evolving melts undergoing crystal fractionation involving plagioclase and amphibole. Abundances and ratios of many trace elements frequently show variations between different sectors within single grains, even where there is no visible sector zoning in cathodoluminescence (CL) imaging. Substitution mechanisms, as reflected in the molar (Sc + Y + REE³⁺)/P ratio, differ in the same growth zone between the sides (along a-axis and b-axis: values approaching 1.0) and tips (c-axis: values between 1.5 and 5.0) of single crystals. These observations have implications for the use of zircons for tracking magmatic processes, particularly in techniques where CL zonation within crystals is not assessed and small analytical spot sizes cannot be achieved. These observations also limit applicability of the widely used Ti-in-zircon thermometer. The age spectra for the Ongatiti and Kidnappers/Rocky Hill samples indicate that both magmatic systems were newly built in the time-breaks after respective previous large eruptions from Mangakino. Trace element variations defining three-component mixing suggest that zircons, sourced from multiple melts, contributed to the population in each system.     

pp′-DDT adsorption to suspended particulate matter in sea water

A procedure was devised to study pp′-DDT [2,2-bis($\text{p-}\text{chlorophenyl}$)-1,1,1-trichloroethane] adsorption and desorption to suspended particulates in aqueous solutions. DDT adsorption to a marine sediment, sediment fractions, clay and humic acid suspended in sea water was investigated and the humic fraction was found to have a greater adsorbing capacity than the clay or sediment. Removal of the humic fraction from sediment reduced the adsorption capacity to less than 60 per cent of the original sediment sample. It was concluded that suspended humic particulates may be important agents for transporting chlorinated hydrocarbons through the water column and for concentrating them in sediments and in detritus-feeding organisms.     

Hydrogen speciation in synthetic quartz

The dominant hydrogen impurity in synthetic quartz is molecular H₂O. H-OH groups also occur, but there is no direct evidence for the hydrolysis of Si-O-Si bonds to yield Si-OH HO-Si groups. Molecular H₂O concentrations in the synthetic quartz crystals studied range from less than 10 to 3,300 ppm (H/Si), and decrease smoothly by up to an order of magnitude with distance away from the seed. OH^? concentrations range from 96 to 715 ppm, and rise smoothly with distance away from the seed by up to a factor of three. The observed OH^? is probably all associated with cationic impurities, as in natural quartz. Molecular H₂O is the dominant initial hydrogen impurity in weak quartz. The hydrolytic weakening of quartz may be caused by the transformation H₂O + Si-O-Si → 2SiOH, but this may be a transitory change with the SiOH groups recombining to form H₂O, and the average SiOH concentration remaining very low. Synthetic quartz is strengthened when the H₂O is accumulated into fluid inclusions and cannot react with the quartz framework.