Late Pleistocene terrestrial climate records in India may be preserved in oxygen and carbon stable isotopes in pedogenic calcrete. Petrography shows that calcrete nodules in Quaternary sediments of the Thar Desert in Rajasthan are pedogenic, with little evidence for postpedogenic alteration. The calcrete occurs in four laterally persistent and one nonpersistent eolian units, separated by colluvial gravel. Thermoluminescence and infrared- and green-light-stimulated luminescence of host quartz and feldspar grains gave age brackets for persistent eolian units I–IV of ca. 70,000–60,000, ca. 60,000–55,000, ca. 55,000–43,000, and ca. 43,000–∼25,000 yr, respectively. The youngest eolian unit (V) is <10,000 yr old and contains no calcrete. Stable oxygen isotope compositions of calcretes in most of eolian unit I, in the upper part of eolian unit IV, and in the nonpersistent eolian unit, range between −4.6 and −2.1‰ PDB. These values, up to 4.4‰ greater than values from eolian units II and III, are interpreted as representing nonmonsoonal18O-enriched “normal continental” waters during climatic phases when the monsoon weakened or failed. Conversely, 25,000–60,000-yr-old calcretes (eolian units II and III) probably formed under monsoonal conditions. The two periods of weakened monsoon are consistent with other paleoclimatic data from India and may represent widespread aridity on the Indian subcontinent during isotope stages 2 and 4. The total variation in δ13C is 1.7‰ (0.0–1.7‰), and δ13C covaries positively and linearly with δ18O. δ13C values are highest when δ18O values indicate the most arid climatic conditions. This is best explained by expansion of C4grasses at the expense of C3plants at low latitudes during glacial periods when atmospheric pCO2was lowered. C4dominance was overridingly influenced by global change in atmospheric pCO2despite the lowered summer rainfall.

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The calcretes in the Thar desert occur in a variety of settings, including the piedmonts, sheetwash aggraded plains; and this study adds calcretes in regolith and colluvio-alluvial plains to the group of settings in which calcretes occur in the region. Field logs, morphological details and analytical data such as petrographic, cathodoluminescence and geochemical characteristics are described along with a discussion on their implications. Sand dunes and sandy plains dating to < 20 ka have weakly developed calcretes. The better-developed calcrete horizons occur in piedmonts, interdunes or in areas that have sufficient groundwater. Deep sections in the region show phases of calcrete development in aeolian sand aggradation at ∼ 150, ∼ 100, ∼ 60 and 27-14 ka. The extensive sheetwash plains have mature calcretes and date to mid-Pleistocene. Our studies indicate that these calcretes represent a hybrid process, where carbonate enrichment of the originally calcareous host occurred due to periodically raised groundwaters, and its differentiation into nodules occurred under subaerial environment i.e., after recession of groundwater. Deep sections also show a stack of discrete calcretes that developed in individual aggradation episodes with hiatuses as indicated by ESR dating results. Nodules display a multiplicity of carbonate precipitation events and internal reorganization of calcitic groundmass. The process is accompanied by degradation and transformation of unstable minerals, particularly clays and with a neosynthesis of palygorskite. The ancient calcretes are dated from the beginning of the Quaternary to ∼ 600 ka and show more evolved morphologies marked by brecciation, dissolution, laminar growth on brecciated surfaces, pisolites and several generations of re-cementation. Mica/chlorite schists and such other rocks are particularly vulnerable to replacement by carbonate. In an extreme case, replacement of quartzose sandstone was observed also. The presence of stretches of alluvio-colluvial plains in an area presently devoid of drainage bespeaks of occasional high-energy fluvial regime, under a semi-arid climate. The mid-Pleistocene period saw a shift towards more arid climate and this facilitated sheetwash aggradation. Finally, during the late Pleistocene, aggradation of aeolian sands indicated a progressively drier climate. However, this does not find its reflection in stable isotope data. The amount of carbonate in the form of calcretes is substantial. The present studies indicate that aeolian dust or rainwater are minor contributors to the carbonate budget. A more important source was provided by the pre-existing calcretes in the sheetwash aggraded plains and detrital carbonate in the aeolian sediments. The original source of carbonate in the region, however, remains unresolved and will need further investigations. Electron spin resonance protocols for the dating of calcretes were developed as a part of this study and the results accorded well with geological reasoning.

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A novel microwave-assisted combustion method was used to prepare Ni powder. The method involves the combustion reaction of nickel nitrate and urea as a fuel in the microwave field. The initiation of the exothermic peak of the combustion reaction was found to vary as a function of urea content. The microwave-prepared Ni powder was characterized using x-ray diffraction (XRD), scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, thermogravimetric (TG) analysis, differential thermal analysis (DTA), and magnetic measurement. The XRD pattern revealed that the Ni powder crystallizes with the cubic phase when the molar ratio of fuel to nitrate is varied between 5:1 and 6:1. Above or below that molar ratio, NiO phase coexists as an impurity along with the Ni phase. The magnetization value of Ni measured at room temperature is 53.5 Am2/kg, which is close to the value observed for commercial Ni powder (55.0 Am2/kg). The mechanism for the formation of the Ni and NiO phase is discussed based on the infrared, TG, and DTA data. The method shows that highly pure Ni powder can be prepared using urea as a fuel and microwaves as a source of energy via the solution combustion method.

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This article focuses on the mechanically induced reactivity of boehmite prepared by thermal decomposition of gibbsite. Boehmite, which retained the morphology of gibbsite, was characterized by a specific surface area of 264 m 2 /g. Mechanical activation (MA) was carried out in a planetary mill up to 240 minutes. The samples were characterized in terms of morphology, characteristic particle diameters, Brunauer Emmett Teller (BET) specific surface area (SSA BET ), microcrystallite dimension (MCD), microstrain (e) and Fourier transform infrared spectroscopy. The reactivity was construed from the kinetics of thermal transformation of boehmite into c-Al 2 O 3 . The transformation observed between 600 K and 900 K (327°C and 627°C), manifested itself as two overlapping peaks in the differential thermogravimetric plot. These peaks correspond to two stages of dehydroxylation involving Al 2 OH and AlOH groups in succession. The peaks were resolved using Gaussian deconvolution. The reactivity was assessed separately for the two stages by comparing the fraction reacted in MA samples (a) with that of nonactivated sample (a ref ). During both stages, enhanced kinetics, as revealed by a-a ref plots, indicated an increase in reactivity with MA. The transformation mechanism conformed to n th order reaction (f[a] = [1 -a] n with n = 1.3-1.5 in both stages). Values of n remained similar for the activated and reference samples. Activation energies (E a ) for the first and second dehydroxylation stages were respectively 115 and 300 kJ/mol for the nonactivated sample. E a for the second stage decreased exponentially to a value of 222 kJ/mol after 240 minutes of milling. An anomalous negative correlation between reactivity and SSA BET was observed. Reactivity parameters were strongly correlated with MCD and e. A plausible explanation for the observed correlations is presented.