Effect of fuel molecules on properties and activity of KOH/calcium aluminate nanocatalyst for biodiesel production

New technologies such as microwaves have gained a large deal of attention from scientists and industries who sought increased rate of production processes. In this study, microwave irradiation was utilized to produce a novel KOH/Ca₁₂Al₁₄O₃₃ nanocatalyst used for biodiesel production. As support, calcium aluminate was prepared by microwave combustion method using different fuels including urea, glycine, sorbitol, and citric acid. The samples were then impregnated by KOH to improve their catalytic activities for microwave-enhanced transesterification of canola oil for biodiesel production. Results of XRD, BET, FTIR, TG, EDX, and FE-SEM analyses showed differences in physicochemical properties of the samples when using different fuels with different flame characteristics and combustion temperatures. Only the urea-fueled sample showed the crystalline structure of monocalcium aluminate (CaAl₂O₄), with the other samples exhibiting amorphous structure of CaO–Al₂O₃. However, all samples, except for that prepared by citric acid, transformed to crystalline structure of Ca₁₂Al₁₄O₃₃ by calcination during KOH impregnation. Among the samples, the KOH/Ca₁₂Al₁₄O₃₃ nanocatalyst prepared by sorbitol showed the highest activity in microwave-enhanced biodiesel production because of its large surface area, pore size, and basicity, converting 93.4% of canola oil to biodiesel at a methanol-to-oil molar ratio of 18, catalyst concentration of 4 wt%, and microwave output power of 450 W in 60 min of reaction time. Moreover, the sample showed well-distributed particle sizes without any agglomeration, so that it could easily maintain its level of activity for several rounds of use.     

Crystal structures and cation distributions in simple spinels from powder XRD structural refinements: MgCr2O4, ZnCr2O4, Fe3O4 and the temperature dependence of the cation distribution in ZnAl2O4

The crystal structure and cation distributions in the spinels MgCr₂O₄, ZnCr₂O₄, Fe₃O₄ and a suite of ZnAl₂O₄ samples annealed at 900 to 1400° C and then rapidly quenched, have been determined by powder X-ray diffraction, using several different X-ray procedures and both conventional structure-factor refinement and whole-pattern (or Rietveld) refinement methods. The chromite spinels are expected from crystal chemical considerations to have an almost completely normal cation distribution (inversion parameter, x, equal to zero). In agreement with this expectation, three samples of MgCr₂O₄ annealed at 900, 1100 and 1300° C, and ZnCr₂O₄ were all found to have x=0 within two estimated standard deviations (esd), suggesting that the accuracy with which cation distributions in spinels may be determined by powder XRD is close to the estimated precision. Slightly better results are obtained assuming neutral-atom scattering curves rather than half-ionized or fully ionized, but the differences are small (within the esd). The results from the Rietveld refinements are similarly in good agreement with those using the conventional structure factor refinement approach (agreement within the combined esd's), although in detail the Rietveld procedure sometimes produces small systematic differences in refined parameters. The suite of ZnAl₂O₄ spinels show a smooth increase in x from 0.01 at 900° C to 0.05 at 1300° C, and this behaviour is well described by the simple thermodynamic model for disordering in spinels with α_Zn-Al=89 kJ/mol, assuming β=?20 kJ/mol. The oxygen positional parameters for Fe₃O₄ are similar to those from published single crystal studies, indicating that the powder method also yields accurate interatomic distances in spinels.     

铬铁矿中亚铁的测定方法

采用硫-磷混合酸微波消解对难溶的钒钛磁铁矿进行前处理,用5-溴-PADAP-过氧化氢分光光度法测定矿样中的钒,优化了微波消解的实验条件。加入浓磷酸和40 g/L氟化钠溶液分别消除了共存常量元素铁和钛的干扰。方法检出限为0.004μg/mL,线性范围为0.01~1.0μg/mL。应用于实际钒钛磁铁矿样品中钒的测定,重现性好,检出限较低,灵敏度较高,能够满足简单、快速、批量分析的要求。     

NMR studies of the leucite analogues X2YSi5O12, where X= K,Rb, Cs; Y = Mg,Zn, Cd

A number of leucite group materials with the formula X₂YSi₅O₁₂ where X=K, Rb, Cs and Y=Mg, Zn, Cd have been synthesized by dry and hydrothermal crystallization of glass starting materials. ²⁹Si MASNMR has been used to obtain structural information, such as the number of distinct tetrahedral sites, degree of cation ordering, and estimates of the mean T-O-T bond angles of the tetrahedra. X-ray powder diffraction gave information on cell volumes and degree of distortion from cubic symmetry for all the samples and space group and structural information for some samples. Integration of the different length-scale data obtained using these two complementary techniques allows greater reliance to be placed on the structures deduced for these leucite samples, which are only available as fine-grained powders. Hydrothermally synthesized K₂MgSi₅O₁₂, K₂ZnSi₅O₁₂ and Rb₂ZnSi₅O₁₂ have structures with 12 distinct tetrahedral sites (T-sites) and are monoclinic P2₁/c while the dry-synthesized equivalents are disordered with single T-sites and are cubic, Ia3d. Most of the other members of the group have structures with 6 tetrahedral sites with Cs₂CdSi₅O₁₂ being orthorhombic, Pbca. Cs₂ZnSi₅O₁₂ has an intermediate “5+2” structure. Decreasing the size of the X⁺ cation for a given Y²⁺ cation gives more collapsed and distorted frameworks. ¹³³Cs NMR was used to show that samples with 6 T-sites have 2 alkali sites. It is deduced that samples with 12 T-sites will undergo a displacive phase transition to a 6 T-site structure (possibly via a 5+2 intermediate in some cases) with no change in the framework topology or degree of T-site ordering.     

C1-C4 hydrocarbons in hydrothermal gases

Twenty-two gas samples from Yellowstone National Park have been analyzed for C₁–C₄ hydrocarbons. All five alkanes in the sequence were identified, two alkenes were identified, and no alkynes were observed. The molecular species present in those samples and the quantitative distribution of those species seems more consistent with an organic orgin (e.g. the thermal degradation of kerogen. etc.) for the hydrothermal gases than with the non-biological production of methane (CO₂ + 4H₂ = CH₄ + 2H₂O) followed by pyrolysis. The latter possibility cannot be completely eliminated, however, since the conditions of reaction are not well known.     

Thorium mineralization in hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton,Kola Peninsula

The Lovozero pluton (Kola Peninsula, Russia) is an unique object from the standpoint of the abundance, diversity, and originality of Th mineralization. In contrast to other igneous rocks and to such chemical elements as Ca, REE, U, and Na, Th in the hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton commonly occurs as its own mineral phases. Umbozerite Na₃Sr₄Th(Mn,Zn,Fe,Mg)[Si₈O₂₄](OH) (7 samples), Ti-Th silicate Na_0–7Sr_0–1ThTi_1–2Si₈O_22–23(OH) · nH₂O (8 samples), Na-Th silicate (Na,K)₄Th₃[Si₈(O,OH)₂₄] · nH₂O (6 samples), thorite (2 samples), steenstrupine-(Ce)-thorosteenstrupine series minerals (5 samples), and Th phosphate (Th,Na,K,Ca,Mg,U,Sr,Ba)[(P,Si, Al)₁O₄] · nH₂O (1 sample) were investigated in this study. Ti-Th silicates and Th phosphate have been described for the first time. All of the above-mentioned minerals have been examined with electron microprobe, IR spectroscopy, powder diffraction, thermogravimetric and optical methods. High-Th minerals such as steenstrupine, umbozerite, Th phosphate, and Na-Th silicates crystallized mainly during the ussingite stage of the pegmatite-forming process. At the early hydrothermal high-alkaline stage, steenstrupine was replaced with REE and Th aggregates (belovite, vitusite, seidite, Na-Th silicates, Ti-Th silicates, etc.). Thorite, Ti-Th silicates, and minerals of the rhabdophane and monazite groups were formed at the late hydrothermal low-alkaline stage. Despite the metamict features of almost all samples, stoichiometric ratios of cations in umbozerites and Ti-Th silicates remain stable. Clear relationships have been revealed between umbozerites and Ti-Th silicates, on the one hand, and seidite-(Ce), a Ti-silicate that has a zeolite-like structure, on the other. This implies that, under certain conditions, these minerals may be regarded as potential suppliers of Th to the environment due to the leaching of Th from zeolite channels.     

Lightning-strike fusion of gabbro and formation of magnetite-bearing fulgurite, Cornone di Blumone, Adamello, Western Alps, Italy

The Adamello gabbro exposed on the summit of Cornone di Blumone, Western Alps, Italy, has been fused by lightning strikes to form magnetite-rich fulgurites produced by melting of magnetite, hornblende, calcic plagioclase and minor clinopyroxene. The composition of quench magnetite in the fulgurite is 44.4 Fe₃O₄; 27.5 MgFe₂O₄; 15.1 FeAl₂O₄; 7.9 Fe₂TiO₄; 2.5 Fe₂SiO₄; 1.9 CaFe₂O₄; 0.8 MnFe₂O₄ and is inferred to have crystallized from a low-Si, Fe-rich melt under high oxidation conditions of about 1 log unit below the log₁₀?O₂ of hematite–magnetite. The low Si, Fe-rich melt is considered to have been produced from fusion of magnetite + hornblende-rich areas of the host gabbro and/or possible separation of an immiscible high Fe₂O₃/FeO Fe-rich, low-Si melt from a more siliceous glass during superheating. Skeletal-dendritic morphologies of magnetite in the fulgurite indicate crystallization under conditions of extreme supercooling. Juxtaposition of areas exhibiting different growth habits and crystal sizes of magnetite may reflect compositionally different local melt domains and/or small differences in the delicate balance between nucleation and growth in domains that had slightly different, although ultrafast, cooling rates.     

Intrinsic oxygen fugacity measurements on seven chondrites,a pallasite,and a tektite and the redox state of meteorite parent bodies

Intrinsic oxygen-fugacity (fO₂) measurements were made on five ordinary chondrites, a carbonaceous chondrite, an enstatite chondrite, a pallasite, and a tektite. Results are of the form of linear log $\text{f}\text{O}{}_2\text{?}\text{1}\text{T}$ plots. Except for the enstatite chondrite, measured results agree well with calculated estimates by others.The tektite produced fO₂ values well below the range measured for terrestrial and lunar rocks. The lowpressure atmospheric regime that is reported to follow large terrestrial explosions, coupled with a very high temperature, could produce glass with fO₂ in the range measured.The meteorite Salta (pallasite) has low fO₂ and lies close to Hvittis (E6). Unlike the other samples, results for Salta do not parallel the iron-wüstite buffer, but are close to the fayalite-quartz-iron buffer in slope.Minor reduction by graphite appears to have taken place during metamorphism of ordinary chondrites. fO₂ values of unequilibrated chondrites show large scatter during early heating suggesting that the constituent phases were exposed to a range of fO₂ conditions. The samples equilibrated with respect to fO₂ in relatively short time on heating. Equilibration with respect to fO₂ in ordinary chondrites takes place between grades 3 and 4 of metamorphism. Application of P ? T ? fO₂ relations in the system C-CO-CO₂ indicates that the ordinary chondrites were metamorphosed at pressures of 3–20 bars, as it appears that they lay on the graphite surface.A steep positive thermal gradient in a meteorite parent body lying at the graphite surface will produce thin reduced exterior, an oxidized near-surface layer, and an interior that is increasingly reduced with depth; a shallow thermal gradient will produce the reverse. A body heated by accretion on the outside will have a reduced exterior and oxidized interior. Meteorites from the same parent body clearly are not required to have similar redox states.     

The stability and compressibility of MgAl2O4 high-pressure polymorphs

High-pressure and high-temperature experiments using a laser-heated diamond anvil cell (LHDAC) and synchrotron X-ray diffraction have revealed a phase transition in MgAl₂O₄. CaTi₂O₄-type MgAl₂O₄ was found to be stable at pressures between 45 and at least 117 GPa. The transition pressure of CaTi₂O₄-type phase in MgAl₂O₄ is much lower than that in the natural N-type mid-oceanic ridge basalt composition. The Birch–Murnaghan equation of state for CaTi₂O₄-type MgAl₂O₄ was determined from the experimental unit cell parameters with K ₀=219(±6) GPa, K ₀′=4(constrained value), and V ₀=238.9(±9) ų. The observed compressibility was in agreement with the theoretical compressibility calculated in a previous study. ε-MgAl₂O₄ was observed at pressures between 40 and 45 GPa, which has not been reported in natural rock compositions. The gradient (dP/dT slope) of the transition from the ε-type to CaTi₂O₄-type MgAl₂O₄ had a positive value. These results should resolve the dispute regarding the stable high-pressure phase of MgAl₂O₄, which has been reported in earlier studies using both the multi-anvil press and the diamond anvil cell.     

Viscosity-temperature relationships in the system Na2Si2O5-Na4Al2O5

The viscosity-temperature relationships of five melts on the join Na₂Si₂O₂-Na₄Al₂O₅ (5, 10, 20, 30 and 40 mole percent Na₄Al₂O₅) have been measured in air, at 1 atm and 1000–1350°C with a concentric cylinder viscometer. All the melts on this join of constant bulk polymerization behave as Newtonian fluids, in the range of shear rates investigated, and the melts exhibit Arrhenian viscosity-temperature relationships.Isothermal viscosities on this join initially decrease and then increase with increasing mole percent Na₄Al₂O₅. The minimum viscosity occurs near 20 mole percent Na₄Al₂O₅ at 1000°C and moves to higher Na₄Al₂O₅ content with increasing temperature.The observation of a viscosity minimum along the join Na₂Si₂-O₅-Na₄Al₂O₅ is not predicted based on earlier viscosity data for the system Na₂O-Al₂O₃-SiO₂ (RlEBLlNG, 1966) or based on calculation methods derived from this and other data (Bottinga and Weill, 1972). This unexpected behavior in melt viscosity-temperature relations emphasizes the need for a more complete data set in simple silicate systems.Previous spectroscopic investigation of melts on the join Na₂2Si₂O₅-Na₄Al₂O₅ offer a structural explanation for the observed viscosity data in terms of a disproportionation reaction involving polyanionic units. Macroscopically, the viscosity data may be qualitatively reconciled with the configurational entropy model for viscous flow (Richet, 1984).     

Application of magnetic adsorbent with silicate and phenyl polymers to adsorb Rhodamine B

The extensive use of Rhodamine B (RhB) for textile, paper, pigment, food, cosmetic, and drug manufacturing and its indiscriminate disposal leads to serious human, biological, and environmental hazards. A magnetic adsorbent with silicate and phenyl polymers (Ph/SiO₂/Fe₃O₄) has been prepared to absorb RhB. The morphology and structure of the adsorbents have been characterized by TGA, XRD, FTIR, and adsorption–desorption measurement. The results revealed that Ph/SiO₂/Fe₃O₄ exhibited a paramagnetic behavior and could easily and quickly be separated from a suspension. The RhB adsorption behavior was almost pH independent due to the adsorption between the phenyl ring of Ph/SiO₂/Fe₃O₄ and RhB by π–π electron-donor–acceptor interactions. The adsorption behavior of RhB adsorption was in good agreement with the Langmuir adsorption isotherm, and the maximum adsorption capacity was 142.186 mg g^?1. Good desorption performance of Ph/SiO₂/Fe₃O₄ showed that this novel magnetic adsorbent cannot only be activated by ethanol extraction process but also reuse by the recovery of magnetic force.     

High-pressure stability, structure and compressibility of Cmcm -MgAl2O4: an ab initio study

 Quantum-mechanical solid-state calculations have been performed on the highest-pressure polymorph of magnesium aluminate (CaTi₂O₄-type structure, Cmcm space group), as well as on the low-pressure (Fd3ˉm) spinel phase and on MgO and Al₂O₃. An ab initio all-electron periodic scheme with localized basis functions (Gaussian-type atomic orbitals) has been used, employing density-functional-theory Hamiltonians based on LDA and B3LYP functionals. Least-enthalpy structure optimizations in the pressure range 0 to 60 GPa have allowed us to predict: (1) the full crystal structure, the pV equation of state and the compressibility of Cmcm-MgAl₂O₄ as a function of pressure; (2) the phase diagram of the MgO–Al₂O₃–MgAl₂O₄ system (with exclusion of CaFe₂O₄-type Pmcn-MgAl₂O₄), and the equilibrium pressures for the reactions of formation/decomposition of the Fd3ˉm and Cmcm polymorphs of MgAl₂O₄ from the MgO + Al₂O₃ assemblage. Cmcm-MgAl₂O₄ is predicted to form at 39 and 57 GPa by LDA and B3LYP calculations, with K ₀=248 (K′=3.3) and 222 GPa (K′=3.8), respectively. Results are compared to experimental data, where available, and the performance of different DFT functionals is discussed. Received: 31 January 2001 / Accepted: 16 May 2001     

Characterization of leached layers on olivine and pyroxenes using high-resolution XPS and density functional calculations

High-resolution core level and valence band (VB) X-ray photoelectron spectra (XPS) of olivine [(Mg_0.87Fe_0.13)₂SiO₄], bronzite [(Mg_0.8Fe_0.2)₂Si₂O₆] and diopside [Ca(Mg_0.8Fe_0.2)Si₂O₆] were collected before and after leaching in pH ∼2 solutions with the Kratos magnetic confinement charge compensation system which minimizes differential charge broadening. The leached samples yield Si 2p, Mg 2p, Ca 2p and O 1s XPS spectral linewidths and lineshapes similar to those collected from the respective pristine samples prior to leaching. As with previous XPS studies on crushed samples, our broadscan XPS spectra show evidence for initial, preferential leaching of cations (i.e., Ca²⁺ and Mg²⁺) from the near-surface of these minerals. The O 1s spectra of leached olivine and pyroxenes show an additional peak due to OH⁻, which arises from H⁺ exchange with near-surface cations (Ca²⁺ and Mg²⁺) via electrophilic attack of H⁺ on the M-O-Si moiety to produce the H₂Mg(M1)SiO_4(surf) complex at olivine surfaces, and two complexes, H₂Mg(M1)Si₂O_6(surf) and H₄Si₂O_6(surf) at diopside and enstatite surfaces. The olivine and pyroxene surface complexes H₂Mg(M1)SiO_4(surf) and H₂Mg(M1)Si₂O_6(surf) have been proposed previously, but the second pyroxene surface complex H₄Si₂O_6(surf) has not. Two electrophilic reactions occur in both olivine and pyroxene. For olivine, the more rapid attacks the M2-O-Si moiety producing H₂Mg(M1)SiO_4(surf); while the second attacks the M1-O-Si moiety ultimately producing H₄SiO₄ which is released to solution. For pyroxenes, the first electrophilic reaction produces H₂Mg(M1)Si₂O_6(surf), while the second produces.H₄Si₂O_6(surf). These two reactions are followed by a nucleophilic attack of H₂O (or H₃O⁺) on Si of H₄Si₂O_6(surf). This reaction is responsible for rupture of the brigding oxygen bond of the Si-O-Si moiety and release of H₄SiO₄ to solution. The intensity of the OH⁻ peak for the leached pyroxenes is about double the OH⁻ intensity for the leached olivine, consistent with the equivalent of about a monolayer of the above surface complexes being formed in all three minerals.Valence band XPS spectra and density functional calculations demonstrate the remarkable insensitivity of the valence band to leaching of Ca²⁺ and Mg²⁺ from the surface layers. This insensitivity is due to a dearth of Ca and Mg valence electron density in the valence band: the Ca-O and Mg-O bonds are highly ionic, with metal-derived s orbital electrons taking on strong O 2p character. The valence band spectrum of leached olivine shows an additional very weak peak at about 13.5 eV, which is assigned to Si 3s valence orbitals in the surface complex H₂Mg(M1)SiO₄, as indicated by high quality density functional calculations on an olivine where Mg²⁺ in M2 is replaced by 2H⁺. The intensity of this new peak is consistent with formation of the equivalent of a monolayer of the surface complex.     

Structure and lattice vibrations of Mg-Al spinel solid solution

X-ray structure refinements have been made for nonstoichiometric (MgO · 3Al₂O₃) and stoichiometric Mg-Al spinels. Several structure variations with chemical composition have been observed and are discussed in relation to Al substitution in tetrahedral sites. Infrared reflection and Raman spectra of the single crystal of the nonstoichiometric spinel (MgO · 3Al₂O₃) have been measured and analyzed. The results obtained are compared with those reported for the stoichiometric sample. From the infrared and Raman frequencies reported for the stoichiometric Mg-Al spinel, which are partly complemented with our results, the effective ionic charges of the ions in MgAl₂O₄ have been estimated on the basis of the rigid ion model.     

The H2O+ Contents of Some Geochemical Standards Predicted by a Calibration Line

The combined water (H₂O⁺) in 30 geochemical standards having known and unknown water contents was determined by an elemental analyzer on 1 day during each of 6 weeks over a period of several months. The analysis of variance of the data measured in the form of a Youden square shows an extremely significant variation due to some unknown cause during the weeks in which the data were obtained. The higher water contents of the first two sets were obtained in the fall season when this area (Reston, Va.) has high and variable humidity, whereas the last four sets were measured during winter months. Humidity, however, was not included as a variable in the design and was not measured. The first two of three average blanks for H₂O⁺, measured after determining H₂O⁺ contents of about 11 percent for two samples, are noticeably higher than the third average blank. Similarly, the first of two average blanks for H₂O⁺, measured after determining the H₂O⁺ content (4.70 percent) of PCC-1, is higher than the second. Data for the last 4 weeks were used to calculate the line of regression and the extremely significant correlation coefficient. The line is used to predict suggested revisions of the “best” H₂O⁺ contents of the standards. Coefficients of variation calculated from the data for the last 4 weeks indicate that there is no severe sampling problem due to the small sample size (20 mg) taken for the determinations. The coefficients follow the general trend of large coefficients for samples containing the least amount of the constituent (BHVO-1: x?= 11.76% H₂O⁺; C.V. = 7.3%) and of small coefficients for samples containing the greatest amount (BX-N: x?= 11.76% H₂O⁺; C.V. = 0.4%).     

Mössbauer and high field magnetization studies of the solid solution CoFexAl2-xO4

By means of paramagnetic Mössbauer spectra the cation distribution of the solid solution CoFe _x Al_2?x O₄ with 0≦x≦1.5 has been determined. The existence of high field magnetic susceptibility at low temperature for samples with x≧0.4 has been interpreted in terms of non-collinear ferrimagnetic arrangements. Below the Neel temperature the spinel CoAl₂O₄ has a complex antiferromagnetic behavior.     

Extraction of molybdenum from spent catalyst by salt-roasting

Spent hydro-refining catalysts mainly consists of 20–22% MoO₃, 5–6% NiO, 4–5% S, 1–2% Co₃O₄, 1.3–1.5% Fe₂O₃, 3–4% SiO₂, and the balance is Al₂O₃. In the present study, one such spent catalyst was roasted with sodium chloride to recover molybdenum by converting it into sodium molybdate. The sodium molybdate was further purified by chemical treatment to obtain a pure grade molybdenum trioxide. Various parameters like temperature, time and NaCl addition have been studied, and conditions for the maximum recovery of molybdenum have been established.     

Geochemistry of Mansar Lake sediments, Jammu, India: Implication for source-area weathering, provenance, and tectonic setting

The sediment geochemistry, including REE, of surface and core samples from Mansar Lake, along with mineralogical investigations, have been carried out in order to understand the provenance, source area weathering, hydrolic sorting and tectonic setting of the basin. The geochemical signatures preserved in these sediments have been exploited as proxies in order to delineate these different parameters.The major element log values (Fe₂O₃/K₂O) vs (SiO₂/Al₂O₃) and (Na₂O/K₂O) vs (SiO₂/Al₂O₃) demarcate a lithology remarkably similar to that exposed in the catchment area. The chondrite normalized REE patterns of lake samples are similar to Post Archaean Australian Shale (PAAS) with LREE enrichment, a negative Eu anomaly and almost flat HREE pattern similar to a felsic and/or cratonic sedimentary source. However, the La–Th–Sc plot of samples fall in a mixed sedimentary domain, close to Upper Continental Crust (UCC) and PAAS, suggesting sedimentary source rocks for the Mansar detritus. It also indicates that these elements remained immobile during weathering and transportation. The mineralogical characteristic, REEs, and high field strength elements (HFSE), together with the high percentage of metamorphic rock fragments in the Siwalik sandstone, support a metamorphic source for lower Siwalik sediments. A very weak positive correlation between Zr and SiO₂, poor negative correlation with Al₂O₃, negative correlation of (La/Yb)_N and (Gd/Yb)_N ratios with SiO₂ and positive correlation with Al₂O₃, suggest that Zr does not dominantly control the REE distribution in Mansar sediments. The petrographic character and textural immaturity indicate a short distance transport for the detritus. The distribution of elements in core samples reflect fractionation. The higher Zr/Th and Zr/Yb ratios in coarse sediments and PAAS compared to finer grained detritus indicate sedimentary sorting. Plots of the geochemical data on tectonic discrimination diagrams suggest that the sediments derived from the lower Siwalik were originated within a cratonic interior and later deposited along a passive margin basinal setting. It therefore reveals lower Siwalik depositional history.     

Temperature-dependent Fe2+–Mn2+ order–disorder behaviour in amphiboles

The partitioning of Fe and Mn between the large M(4) site and the octahedral sites, M(1,2,3) in the amphibole structure has been investigated in two natural manganogrunerites of compositions Ca_0.1Mn_1.9 Mg_1.25Fe²⁺ _3.56Fe³⁺ _0.38Si_7.81O₂₂(OH)₂ and Ca_0.24Mn_1.57 Mg_2.27 Fe²⁺ _2.76Fe³⁺ _0.32Si_7.84O₂₂(OH)₂. The long-range cation distribution in the two samples has been elucidated by in situ neutron powder diffraction revealing that Mn is preferentially ordered onto M(4) ? M(2) >M(1) >M(3) in both samples. Partitioning of Mn from M(4) into the octahedral sites begins at 350 °C, with site exchange energies of ?16.6 kJ mol^?1 and ?14.9 kJ mol^?1, in samples containing 1.90 and 1.57 Mn apfu, respectively. Mössbauer and infrared spectroscopy have been used to study the samples at room temperature, and Mössbauer data agree well with the diffraction results, confirming that high-temperature cation distributions are retained during cooling. The fine structure in the hydroxyl-stretching region of the IR absorption spectra has been used to discuss qualitatively the site occupancies of the coordinating M(1)M(3)M(1) triplet, linked by O(3). On the basis of such modelling, we conclude that a degree of local clustering is present in both samples.     

57Fe-Mössbauer spectroscopy on natural eosphorite-childrenite-ernstite samples

Samples of the eosphorite-childrenite [(Mn²⁺, Fe²⁺)AlPO₄(OH)₂H₂O] series from Divino das Laranjeiras and Araçuaí (Minas Gerais State) and Parelhas (Rio Grande do Norte State) pegmatites have been investigated by X-ray diffraction, microprobe analysis and Mössbauer spectroscopy at 295 and 77 K. The Mössbauer spectra of ernstite [(Mn²⁺, Fe³⁺)AlPO₄(OH)_2-xO_x] showed the existence of ferric ions in both A and B sites, whereas ferrous ions seem to be located exclusively in the A site. Nonoxidised samples show ferrous ions located in both sites, and no Fe³⁺ could be detected. The interpretation of the Mössbauer spectra of both, oxidised and nonoxidised samples, is difficult because the hyperfine parameters of these minerals are rather similar, rendering it difficult to make proper site assignments.