Infrared spectroscopic and X-ray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite

Fourier transformed infrared (FTIR) spectroscopy was used to characterize arsenate-ferrihydrite sorption solids synthesized at pH 3-8. The speciation of sorbed arsenate was determined based on the As-O stretching vibration bands located at 650-950 cm⁻¹ and O-H stretching vibration bands at 3000-3500 cm⁻¹. The positions of the As-O and O-H stretching vibration bands changed with pH indicating that the nature of surface arsenate species on ferrihydrite was strongly pH dependent. Sorption density and synthesis media (sulfate vs. nitrate) had no appreciable effect. At acidic pH (3, 4), ferric arsenate surface precipitate formed on ferrihydrite and constituted the predominant surface arsenate species. X-ray diffraction (XRD) analyses of he sorption solids synthesized at elevated temperature (75 °C), pH 3 clearly showed the development of crystalline ferric arsenate (i.e. scorodite). In neutral and alkaline media (pH 7, 8), arsenate sorbed as a bidentate surface complex (in both protonated FeO₂As(O)(OH)⁻ and unprotonated forms). For the sorption systems in slightly acidic media (pH 5, 6), both ferric arsenate and surface complex were probably present on ferrihydrite. It was further determined that the incorporated sulfate in ferrihydrite during synthesis was substituted by arsenate and was more easily exchangeable with increasing pH.     

Characteristics and origins of lee-side stratification sequences in late pleistocene drumlins,northern Ireland

Spindle- and parabolic-shaped drumlins examined at fifty-five localities in northern Ireland possess stratification sequences on their lee-side flanks. These forms lack the distinctive steep stoss- and tapering lee-ends of classical drumlins and tend to occur in linear zones transverse to late Pleistocene ice-flow. In most cases (90 per cent) the stratified deposits infill embayments excavated in the lee-side of barkhanoid forms and, in the remainder (10 per cent), they are superimposed on the lee-side of whaleback forms. The stratification sequences developed as a result of sedimentation in interconnected subglacial water-filled cavities and are unlike remanie proglacial sediments moulded by ice into drumlin form. Stratigraphic evidence indicates that the lee-side sequences developed during drumlin streamlining, which supports the view that subglacial hydraulic processes played an important role in drumlin formation.     

The transformation and export of phosphorus from Wetlands

There is widespread acceptance of the phosphorus retention capability of wetlands even though research findings are often inconclusive and contradictory. The results of a one year phosphorus budget study indicate that internal wetland processes may transform sediment bound phosphorus to plant available orthophosphorus. While total phosphorus imports were nearly double the total phosphorus exports for the study wetland, orthophosphorus exports were 22 per cent greater than imports. This study supports the recent finding that wetlands have limited capability to retain orthophosphorus and indicates that wetlands may even increase the export of orthophosphorus. The generally accepted nutrient retention function of wetlands and their possible role in eutrophication is thus questionable.     

Assessment of textural variational pattern and electrical conduction of economic and accessible Quaternary hydrolithofacies via geoelectric and laboratory methods in SE Nigeria: A case study of select locations in Akwa Ibom State

Textural variational pattern of economic and accessible Quaternary aquifer repositories and its conductivity in the south-eastern Nigeria have been assessed through the integration of vertical electrical sounding and laboratory measurements. The results have shown the lithological attributes, pore-water and amount of residual clay minerals in the assumed clean sand; mechanism of charge fixation at the fluid - surface interface; intricate geometry of pores and pore channels; formation’s ability to transmit pore-water and cation exchange capacity.The connections of electrical and hydraulic properties and their distributions have been established. The average interface conductivity contributed by residual clay minerals in assumed clean sands of the aquifer repositories in the study area have been estimated as 30µS/m. Intrinsic average porosity and formation factor have been respectively deduced as 12% and 14.75. Comparing the simulated aquifer formation factor obtained from the observed porosity data with the observed aquifer formation factor, indicates the that study area has 0.5 ≤ a ≤ 0.8 pore geometry factor and 1.5 ≤ m ≤ 2.0 cementation factor as the best fitting values. The interrelations between aquifer parameters have been established through different plots and the aquifer have been empirically proved to be associated with residual clay minerals as the interface conductivity C_q is not equal to zero. The wide ranges of parameters estimated are an indication of variations in grain size. The estimated intrinsic average porosity, formation factor and the average BQ_v are viable in characterizing the aquifer flow dynamics and contaminant modelling in the associated aquifer sands For low pore geometry factors a (0.2) and low cementation factor m (0.5) the formation factor remains fairly constant. However, marked variability is noticed at higher a (1.0) and m (2.5). Despite the observed variability in formation factors at the indicated porosities, the spatial or geometrical spread of the formation factor remains unchanged in the aquifer units. The Tables for geoelectric and petrophysical parameters and the associated mathematical models generated in this study can be used for groundwater contaminant modelling and simulation of pore space parameters with reasonable accuracy.     

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.     

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.     

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.