Aqueous uptake of uranium onto pyrite surfaces; reactivity of fresh versus weathered material

In order to better understand the interaction between aqueous uranium and pyrite (FeS₂) the uptake of uranium onto the surfaces of both weathered and freshly generated pyrite surfaces was examined using batch sorption experiments. Analysis was performed using X-ray photoelectron spectroscopy (XPS). The results clearly indicate that freshly polished pyrite surfaces are efficient scavengers of uranium from solution, while weathered surfaces exhibit only limited uptake. Results also indicate partial reduction of uranium at the pyrite surfaces, with a heterogeneous distribution of U(IV) and U(VI) species.     

A microscopic study of synthetic PbS-Rich homologues nPbS-mBi2S3

The PbS-Bi₂S₃ join was studied up to 25 mole percent Bi₂S₃ by electron microscopy and diffraction. It was found that Bi₂S₃ can be incorporated into the PbS matrix by tropochemical twinning, forming isolated {113}_PbS microtwins, or after clustering of these defects, lamellar twinned regions. Only two known mineral members of the homologous series (lillianite Pb₃Bi₂S₆ and heyrowskyite Pb₆Bi₂S₉) were found to be stable in this part of the PbS-Bi₂S₃ join, while irregularly spaced twin bands within these two structures were observed where deviations in the PbS/Bi₂S₃ ratio from 6/1 and 3/1, respectively, took place. No ordered intergrowth members were found between heyrowskyite and lillianite. The difference between the PbS-Bi₂S₃ join and the analogous MnS-Y₂S₃ one was attributed to the lone pair of nonbonded electrons from the Bi³⁺ ions, which tends to concentrate these ions in the vicinity of the twin planes.     

Flotation of calcareous Mussorie phosphate ore

Separation of Mussorie rock phosphate (P₂O₅ = 20%) from Uttar Pradesh, India, containing pyrite, calcite and other carbonaceous impurities by flotation has been successfully attempted to upgrade the phosphate values. Based on Hallimond cell flotation results of single and synthetic mineral mixtures of calcite and apatite using oleic acid and potassium phosphate, conditions were obtained for the separation of calcite from apatite which is considered to be the most difficult step in the beneficiation of calcareous phosphates. Further studies using 250 g of the mineral (?60 +150 and ?150 mesh fractions, deslimed) in laboratory size Fagergren subaeration machine employed a stagewise flotation viz. carbonaceous materials using terpineol, pyrite using potassium-ethyl xanthate and calcite using oleic acid respectively. Separation was, however, found to be unsatisfactory in the absence of a depressant.Among starch, hydrofluosilicic acid and dipotassium hydrogen phosphate, which were tried as depressants for apatite in the final flotation stage, dipotassium hydrogen phosphate proved to be superior to others. However, the tests with the above fractions did not yield the required grade. This was possibly due to insufficient liberation of the phosphate mineral from the ore body and different experimental conditions due to scale up operations. Experiments conducted using ?200 mesh deslimed fractions has yielded an acceptable grade of 27.6% P₂O₅ with a recovery of about 60%. The results have been explained in terms of the specific adsorption characteristics of phosphate ions on apatite and the liberation size of the mineral.     

Hydrometallurgical processing and recovery of molybdenum trioxide from spent catalyst

Hydrometallurgical processing of spent hydrodesulphurisation (HDS) catalyst for the recovery of molybdenum using sodium carbonate and hydrogen peroxide mixtures was investigated. The results indicated that the recovery of molybdenum was largely dependent on the concentrations of Na₂CO₃ and H₂O₂ in the reaction medium, which controls the acidity of the leach liquor and carry over of impurities such as Al, Ni, P, Si and V. Leaching process was exothermic and leaching efficiency of molybdenum decreased with increasing solid to liquid ratio. Large scale leaching of spent catalyst, under optimum conditions: 20% pulp density, 85 g/L Na₂CO₃, 10 vol.% H₂O₂ and 1 h reaction, resulted a leaching efficiency of 84% Mo. The obtained leach liquor contained (g/L): Mo — 22.0, Ni — 0.015 and Al — 0.82, P — 1.1, Si — 0.094 and minor quantities of V — 8 mg/L, As and Co — < 1 mg/L. Recovery of Mo from leach solution as MoO₃ of 97.30% purity was achieved by ammonium molybdate precipitation method.     

Infrared reflectivity spectra of single crystal cassiterites

The infrared reflectivity spectra of two natural cassiterite single crystals from Portugal and Vietnam have been studied and analysed in the frequency range of 15–4000 cm^–1 at room temperature. The optical mode parameters are deduced by simulation of the experimental spectra using the factorised form of the dielectric function. The difference with synthetic SnO₂ spectra is a dip near 500 cm^–1 understood as the activation of an infrared forbidden E _g mode due to the amount of Fe³⁺ and Ti⁴⁺ impurities. Another result of this work is the derivation of the correct values of the static dielectric constant of cassiterite.     

Mg2+ removal in the system Mg2+—amorphous SiO2—H2O by adsorption and Mg-hydroxysilicate precipitation

Two chemical processes can remove Mg²⁺ from suspensions containing amorphous silica (am-SiO₂) at low temperatures: adsorption and precipitation of a Mg-hydroxysilicate resembling sepiolite. Mg²⁺ removal from am-SiO₂ suspensions was investigated, and the relative role of the two removal processes evaluated, as a function of: pH, ionic strength, Mg²⁺ concentration, and temperature.The extent of Mg²⁺ adsorption onto am-SiO₂ decreases with increasing NaCl concentration due to displacement of Mg²⁺ by Na⁺. At NaCl concentrations of 0.05 M and above, adsorption occurs only at pH values above 8.5, where rapid dissolution of am-SiO₂ gives rise to high concentrations of dissolved silica, resulting in supersaturation with respect to sepiolite. Removal of Mg²⁺, at concentrations of 40 to 650 μM, from am-SiO₂ suspensions in 0.70 M NaCl at 25 °C occurs at pH 9.0 and above. Experiments show that under these conditions adsorption and Mg-hydroxysilicate precipitation remove Mg²⁺ at similar rates. For 0.05 M Mg²⁺, at 0.70 M ionic strength and 25 °C, measurable Mg²⁺ removal occurs down to ca. pH 7.5 but is primarily due to Mg-hydroxysilicate precipitation. For the same solution conditions at 5°C, Mg²⁺ removal occurs above pH 8.0 and is primarily due to adsorption.Assuming that increasing pressure does not greatly enhance adsorption, Mg²⁺ adsorption onto am-SiO₂ is an insignificant process in sea water. The surface charge of pristine am-SiO₂ in sea water is primarily controlled by interactions with Na⁺. The principal reaction between Mg²⁺ and am-SiO₂ in marine sediments is sepiolite precipitation.The age distribution of sepiolite in siliceous pelagic sediments is influenced by temperatures of bottom waters and by geothermal gradients.     

Large-scale Mechanical Redistribution of Orthopyroxene and Plagioclase in the Basement Sill, Ferrar Dolerites, McMurdo Dry Valleys, Antarctica: Petrological, Mineral-chemical and Field Evidence for Channelized Movement of Crystals and Melt

The Jurassic Ferrar dolerite sills of the McMurdo Dry Valleys,Antarctica represent the plumbing system for flood basalt eruptionsassociated with the breakup of Gondwana. Among the Ferrar sills,the 350–450 m thick cumulate-textured Basement Sill isdifferentiated into a Lower Marginal Zone (LMZ) gabbronorite,a thick Lower Zone (LZ) orthopyroxene–plagioclase orthocumulatepyroxenite, a strongly layered mela- to leuco-gabbronorite MiddleZone (MZ), a thick Upper Zone (UZ) gabbronorite with ferrogabbroicpods, and an Upper Marginal Zone (UMZ) gabbronorite. Texturesand mineral compositions in the LZ pyroxenite and MZ–UZgabbronorites are nearly identical, the main distinction beingthe greater relative proportion of plagioclase in the MZ–UZgabbronorites, and of pigeonite in the UZ. Most orthopyroxenein the LZ, MZ and UZ occurs as sub-euhedral, normally zonedprimocrysts, commonly with rounded plagioclase inclusions. Plagioclaseis usually sub-euhedral and normally zoned, but can containsodic cores interpreted to be xenocrystic. Orthopyroxene andfeldspar compositions thoughout the sill are generally fairlyuniform, and resemble the compositions of micro-phenocrystsin the chilled margins. We infer that the sill was filled bya c. 1250°C slurry of orthopyroxene + plagioclase phenocrystsor primocrysts that subsequently unmixed in response to buoyancyforces. The LZ websterite contains numerous anorthosite to gabbronoriteschlieren, veins and pipes (< 2 m diameter), which we interpretas fossil segregation channels. Textures and mineral compositionsin these felsic channels are very similar both to UZ and MZgabbronorites, and to the groundmass separating accumulatedorthopyroxene primocrysts in the LZ and MZ. We infer that plagioclase-charged,hydrous pore melt from the pyroxenite may have segregated, pooledand ascended through these conduits to feed growth of the UZgabbronorite. Detailed mapping shows that the pipes are separatedby about 15 m on average. Calculations suggest that this numberdensity of conduits could have drained the LZ cumulates of theirinterstitial melt + plagioclase in about 8 days. Sequences (eachc. 5–10 m thick) of layered leuco-gabbronorite in theMZ could represent intra-cumulate sills that formed from plagioclase-richslurries ascending in segregation channels. Fe–Ti-richpyroxenitic veins and pods (some pegmatitic) and an unusualcoarse-grained plagioclase facies occur at the contacts betweenmassive leuco-gabbronorite layers in the MZ. Discordant ferro-pegmatitepods and dykes occur throughout the UZ. We interpret these Fe-richpegmatoidal rocks as evolved residual melts expelled from thecompacting gabbronoritic cumulates of the MZ and UZ. KEY WORDS: Ferrar; cumulates; differentiation; Antarctica; layering     

Geochemical types of Volkhovites and possible diamond resource potential of areas occupied by Holocene fluidisites

Volkhovites—tektite-like glasses—have been detected in the Holocene glacial drift along the right bank of the Volkhov River. A cryptomagmatic model of their formation and pre-Holocene age of volkhovite melts, cinder, and frothed glasses has been suggested (Skublov et al., 2007). Four geochemical types of volkhovites are distinguished: (1) manganous (Mn, Fe, Cr, V, Si, Nb, Pb, H), (2) magnesian (Mg, Al, Ti, F, B), (3) potassic (K, Rb, Cs), and (4) calcic (Ca, REEs, Ba, U, Th, Ta, Hf, Y, Sc, Cl). In light of the geochemical data, volkhovites are regarded as natural silicate glasses of kimberlite-carbonatite composition. Their types are called kimberlitic (Mn type), kimberlitic-carbonatitic (Mg type), lamproitic-carbonatitic (K type), and carbonatitic (Ca type). Volkhovites are suggested to be indicators of undiscovered diamond mineralization of kimberlite or carbonatite (Chagatai) types.     

Composition, sources, and mechanism of continental crust growth in the Lake zone of the Central Asian Caledonides: I. Geological and geochronological data

Data on the composition, inner structure, and age of volcanic and siliceous-terrigenous complexes and granitoids occurring in association with them in the Caledonian Lake zone in Central Asia are discussed in the context of major relations and trends in the growth of the Caledonian continental crust in the Central Asian Foldbelt (CAFB). The folded structures of the Lake zone host basalt, basalt-andesite, and andesite complexes of volcanic rocks that were formed in distinct geodynamic environments. The volcanic rocks of the basalt complex are noted for high concentrations of TiO₂ and alkalis, occur in association with fine-grained siliceous siltstone and siliceous-carbonate rocks, are thus close to oceanic-island complexes, and were likely formed in relation to a mantle hotspot activity far away from erosion regions supplying terrigenous material. The rocks of the basalt-andesite and andesite complexes have lower TiO₂ concentrations and moderate concentrations of alkalis and contain rock-forming amphibole. These rocks are accompanied by rudaceous terrigenous sediments, which suggests their origin in island-arc environments, including arcs with a significantly dissected topography. These complexes are accompanied by siliceous-terrigenous sedimentary sequences whose inner structure is close to those of sediments in accretionary wedges. The folded Caledonides of the Lake zone passed through the following evolutionary phases. The island arcs started to develop at 570 Ma, their evolution was associated with the emplacement of layered gabbroids and tonalitetrondhjemite massifs, and continued until the onset of accretion at 515–480 Ma. The accretion was accompanied by the emplacement of large massifs of the tonalite-granodiorite-plagiogranite series. The postaccretionary evolutionary phase at 470–440 Ma of the Caledonides was marked by intrusive subalkaline and alkaline magmatism. The Caledonides are characterized by within-plate magmatic activity throughout their whole evolutionary history, a fact explained by the accretion of Vendian-Cambrian oceanic structures (island arcs, oceanic islands, and back-arc basins) above a mantle hotspot. Indicators of within-plate magmatic activity are subalkaline high-Ti basalts, alkaline-ultrabasic complexes with carbonatites and massifs of subalkaline and alkaline gabbroids, nepheline syenites, alkaline granites, subalkaline granites, and granosyenites. The mantle hotspot likely continued to affect the character of the lithospheric magmatism even after the Caledonian folded terrane was formed.     

Possible implications of modal mineralogy for melting in mantle lherzolites

The melting reaction at the solidus of mantle peridotite is commonly peritectic in nature, with liquid and one or more solid phases produced upon melting. In some situations, one of the phases participating on the reactant side of the reaction is present in low abundance. This article explores the possible effects of the low abundance of a reactant phase on the melting behavior of mantle peridotite.For example, spinel lherzolite begins to melt via the peritectic reaction, clinopyroxene + orthopyroxene + spinel = olivine + liquid in the ∼1- to 2-GPa pressure range. In natural spinel lherzolites, spinel is a modally minor mineral and may be infrequently in contact with both clinopyroxene and orthopyroxene. If these mutual contacts are insufficient to generate an interconnected melt, then significant melting may not occur until a combination of minerals that are modally abundant and in contact begin to melt. This scenario could have implications for the physical process of melting and for the timing of formation of an interconnected melt network and separation of the melt from the residue.To begin to investigate this possibility, the spatial relationships between the constituent minerals in two fertile spinel lherzolites were determined by elemental mapping with the electron microprobe. Olivine, orthopyroxene, and clinopyroxene are of similar size, whereas the spinel was smaller and interstitial. Spinel and clinopyroxene are frequently in contact, but mutual contacts of spinel, clinopyroxene, and orthopyroxene are rare. Because of the changes in modal mineralogy anticipated for these lherzolites with increasing temperature, these mutual contacts will be even less common at the solidus. Therefore, an interconnected, potentially extractable, melt may not occur by the solidus spinel + orthopyroxene + clinopyroxene melting reaction.