Authigenic quartz and albite in Devonian limestones: origin and significance

Euhedral quartz and albite crystals are common in Devonian (Givetian-Frasnian) shallow-marine shelf carbonates from the Belgian Ardennes. Several features such as morphology, the presence of carbonate inclusions, inversion temperatures and occurrence in the insoluble residues of stylolitic surfaces indicate that these crystals have developed authigenically. Oxygen isotope ratios point to an intermediate deep burial realm of origin at temperatures of 60–90°C. The predominance of illite and the almost total absence of smectite clay minerals is interpreted as an indication that illitization produced the silica needed for authigenesis. The mineral composition of inclusions indicates that the carbonate host rock must have consisted of low-Mg calcite already at the time of authigenesis. These inclusions represent an earlier diagenetic stage than the present carbonate rock, since they were protected from further diagenetic alteration by the surrounding quartz. The calcite inclusions display a higher Sr/Ca and Mg/Ca ratio than the carbonate host-rock. Because neomorphic diagenesis of the carbonate continued after silicate authigenesis, the contents of Mg and Sr in the calcite of the host carbonate are even lower. The authigenic feldspar mineralogy seems to be determined by the composition of the host-sediment.     

Stabilization of clayey soils with Tunisian phosphogypsum: effect on geotechnical properties

Phosphogypsum and cement have been reported to improve the physicochemical properties of clayey soils. The present study aimed to investigate the behavior of various soils with different particle sizes and chemical and mineralogical compositions in the presence of phosphogypsum and cement mixed at various proportions. These hydraulic binders were assayed on three different soil samples, and their effects were examined using a battery of standardized tests, including the Atterberg limit, uniaxial compressive strength, Californian Bearing Rate (CBR) test, thermogravimetric analysis (TGA), microstructure observation (SEM), and X-ray diffraction tests. The results revealed a significant effect associated with the variation of phosphogypsum content in the soils. Keeping the cement content constant in the mixture, the continuous addition of phosphogypsum was noted to allow shifting the domain of plasticity to the highest water contents, which reduces the sensitivity of the soil to water and to increase the strength of soil. An increase of CBR index with the addition of phosphogypsum and cement is obtained. This treatment could have positively influenced the optimum moisture content and the maximal dry density. The mixture of soil-phosphogypsum and cement could give new forms such as ettringite and hydrate indicators of the improvement of the mechanical properties of the soil. This improvement varies from one soil to another, depending on its granularity and its mineralogy. The mineralogical composition of the soil, particularly kaolinite, amount, and size grading, have direct effects on the physical and mechanical properties of the soils under investigation.     

Geochronological and isotopic records of crustal storage and assimilation in the Wolverine Creek–Conant Creek system,Heise eruptive centre,Snake River Plain

Understanding the processes of differentiation of the Yellowstone–Snake River Plain (YSRP) rhyolites is typically impeded by the apparent lack of erupted intermediate compositions as well as the complex nature of their shallow interaction with the surrounding crust responsible for their typically low O isotopic ratios. A pair of normal-δ¹⁸O rhyolitic eruptions from the Heise eruptive centre in eastern Idaho, the Wolverine Creek Tuff and the Conant Creek Tuff, represent unique magmatic products of the Yellowstone hotspot preserving abundant vestiges of the intermediate differentiation steps leading to rhyolite generation. We address both shallow and deep processes of magma generation and storage in the two units by combining high-precision ID–TIMS U–Pb zircon geochronology, trace element, O and Hf isotopic studies of zircon, and Sr isotopic analyses of individual high-Mg# pyroxenes inherited from lower- to mid-crustal differentiation stages. The zircon geochronology confirms the derivation of both tuffs from the same rhyolitic magma reservoir erupted at 5.5941 ± 0.0097 Ma, preceded by at least 92 ± 14 ky of continuous or intermittent zircon saturation approximating the length of pre-eruptive magma accumulation in the upper crust. Some low-Mg# pyroxenes enclosing zircons predate the eruption by at least 45 ± 27 ky, illustrating the co-crystallisation of major and accessory phases in the near-liquidus rhyolitic melts of the YSRP over a significant period of time. Coeval zircon crystals are isotopically heterogeneous (two populations at εHf ~?5 and ?13), requiring the assembly of isotopically distinct melt pockets directly prior to, or during, the eruption. The primitive Mg# 60–90 pyroxenes are out of isotopic equilibrium with the host rhyolitic melt (⁸⁷Sr/⁸⁶Sr_i = 0.70889), covering a range of ⁸⁷Sr/⁸⁶Sr_i = 0.70705–0.70883 corresponding to ratios typical of the most radiogenic YSRP basalts to the least radiogenic YSRP rhyolites. Together with the low εHf in zircon, the Sr isotopic ratios illustrate limited assimilation dominated by radiogenic Archean crustal source materials incorporated into variably evolved YSRP melts as they progress towards rhyolitic compositions by assimilation–fractional crystallisation.     

Pretreatment of high strength waste emulsions by combined vibratory shear enhanced process with Fenton oxidation

Pretreatment of waste emulsions with high organic content by a combined process of vibratory shear enhanced process and Fenton’s oxidation prior to biological treatment was investigated. Vibrating membrane had shown good performance in chemical oxygen demand and oil removals and the mitigation of concentration polarization. However, the permeate after filtration processing still contained high content of organics. Thus, additional Fenton oxidation was applied to reduce the organic loading, and improve the biodegradability of the wastewater. The optimal molar ratio of ferrous iron to hydrogen peroxide was 0.05 obtained from the jar-test experiments. Removal of organics was enhanced by increasing hydrogen peroxide dosage, while efficiency of hydrogen peroxide reached maximum of 1.11(w/w) at the hydrogen peroxide dosage of 6.8 g/L. Furthermore, the biological experiments indicated that the high concentration of organics could inhibit microbial activity, which decreased the chemical oxygen demand degradation rates. The adaptive period of the microbe was greatly shortened using Fenton’s reagent at the low dosages. The improvement of the biodegradability could be explained by partial mineralization and chemical transformation of parent organic compounds after Fenton oxidation.     

Rigid Unit Modes in disordered nepheline: a study of a displacive incommensurate phase transition

 Calculations of the Rigid Unit Modes (RUMs) allowed in the nepheline structure are used to explain the diffuse scattering previously seen in electron diffraction experiments. The RUM calculations also show that the modulation wavelength for incommensurate nephelines is essentially determined by the framework topology. X-ray diffraction is used to measure the intensity of the diffuse scattering as a function of temperature. The diffuse intensity increases sharply at 308 K. This effect is interpreted as being due to the softening of a phonon mode, indicating a phase transition. Measurements of this phase transition below the transition temperature are made using hard mode infrared spectroscopy. Received: 17 February 1999 / Revised, accepted. 15 October 1999     

Compositional controls on spinel clouding and garnet formation in plagioclase of olivine metagabbros,Adirondack Mountains,New York

Olivine metagabbros from the Adirondacks usually contain both clear and spinel-clouded plagioclase, as well as garnet. The latter occurs primarily as the outer rim of coronas surrounding olivine and pyroxene, and less commonly as lamellae or isolated grains within plagioclase. The formation of garnet and metamorphic spinel is dependent upon the anorthite content of the plagioclase. Plagioclase more sodic than An_38±2 does not exhibit spinel clouding, and garnet rarely occurs in contact with plagioclase more albitic than An_36±4. As a result of these compositional controls, the distribution of spinel and garnet mimics and visually enhances original igneous zoning in plagioclase. Most features of the arrangement of clear (unclouded) plagioclase, including the shells or moats of clear plagioclase which frequently occur inside the garnet rims of coronas, can be explained on the basis of igneous zoning. The form and distribution of the clear zones may also be affected by the metamorphic reactions which have produced the coronas, and by redistribution of plagioclase in response to local volume changes during metamorphism.Authors listed alphabeticallyPublished by permission of the Director, New York State Museum, Journal Series Number 299     

Natural manganese oxide: Combined analytical approach for solid characterization and arsenic retention

To understand the retention of As on a natural manganese sand, the structural, textural and chemical properties of the solid were first investigated by combining scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-energy-loss spectroscopy (EELS), X-ray diffraction (XRD), BET N₂ gas adsorption, diffuse reflectance Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis. Manganese sand could be mainly described as a mixture of a phyllomanganate, lithiophorite [(Al,Li)MnO₂(OH)₂], and pyrolusite (MnO₂). Iron particle, kaolinite and gibbsite type-phases were also observed. Particles organization led to the presence of a mesoporosity with pore diameters ranging from 100 to 200 Å and a specific surface area of 23 m² g⁻¹. Contact with an As(V) solution (0.67 mmol L⁻¹) led to an average fractional surface coverage of 0.4. Both As (V) and (III) were present on the surface of the sand in a 1:1 ratio. As(V) was sorbed on lithiophorite-type particles through surface complexation type reaction. As(III) was thought to result from As(V) reduction mechanism on iron particles.     

Sulphide Segregation in Ferropicrites from the Pechenga Complex, Kola Peninsula, Russia

The Palaeoproterozoic Ni–Cu sulphide deposits of the PechengaComplex, Kola Peninsula, occur in the lower parts of ferropicriticintrusions emplaced into the phyllitic and tuffaceous sedimentaryunit of the Pilgujärvi Zone. The intrusive rocks are comagmaticwith extrusive ferropicrites of the overlying volcanic formation.Massive lavas and chilled margins from layered flows and intrusionscontain <3–7 ng/g Pd and Pt and <0·02–2·0ng/g Ir, Os and Ru with low Pd/Ir ratios of 5–11. Theabundances of platinum group elements (PGE) correlate with eachother and with chalcophile elements such as Cu and Ni, and indicatea compatible behaviour during crystallization of the parentalmagma. Compared with the PGE-depleted central zones of differentiatedflows (spinifex and clinopyroxene cumulate zones) the olivinecumulate zones at the base contain elevated PGE abundances upto 10 ng/g Pd and Pt. A similar pattern is displayed in intrusivebodies, such as the Kammikivi sill and the Pilgujärvi intrusion.The olivine cumulates at the base of these bodies contain massiveand disseminated Ni–Cu-sulphides with up to 2 µg/gPd and Pt, but the PGE concentrations in the overlying clinopyroxenitesand gabbroic rocks are in many cases below the detection limits.The metal distribution observed in samples closely representingliquid compositions suggests that the parental magma becamesulphide saturated during the emplacement and depleted in chalcophileand siderophile metals as a result of fractional segregationof sulphide liquids. Relative sulphide liquid–silicatemelt partition coefficients decrease in the order of Ir >Rh > Os > Ru > Pt = Pd > Cu. R-factors (silicate-sulphidemass ratio) are high and of the order of 10⁴–10⁵, andthey indicate the segregation of only small amounts of sulphideliquid in the parental ferropicritic magma. In differentiatedflows and intrusions the sulphide liquids segregated and accumulatedat the base of these bodies, but because of a low silicate–sulphidemass ratio the sulphide liquids had a low PGE tenor and Pt/Irand Cu/Ir ratios similar to the parental silicate melts. Duringcooling the sulphide liquid crystallized 40–50% of monosulphidesolid solution (mss) and the residual sulphide liquid becameenriched in Cu, Pt and Pd and depleted in Ir, Os and Ru. TheCu-rich sulphide liquid locally assimilated components of thesurrounding S-rich sediments as suggested by the radiogenicOs isotopic composition of some sulphide ores (     

Proterozoic copper deposits in NW Queensland,Australia: Sulfur isotopic data

Sulfur isotopic disequilibrium is commonly observed between associated pyrite and copper sulfides in NW Queensland. A sulfur isotopic study of copper mineralization in dolomites at Paradise Valley and arenites at Mammoth has allowed the significance of such disequilibrium to be evaluated. Copper mineralization at Paradise Valley is characterized by a greater enrichment in ³⁴S, with δ³⁴S values often greater than +30‰, for both copper sulfides and associated syngenetic/diagneetic pyrite. At Mammoth, copper sulfides have isotopic compositions (δ³⁴S=?15.9 to ?0.3‰) transitional between disseminated syngenetic/diagenetic pyrite (δ³⁴S=?5.7 to ?1.7‰) and epigenetic vein pyrite (δ³⁴S=?17.9 to ?7.1‰) suggesting progressive reaction and replacement of syngenetic/diagenetic pyrite by a copper-bearing mineralizing fluid under oxidizing conditions. The isotopic data, within the constraints imposed by geological and geochemical factors, support a model of reaction between copper-bearing mineralizing fluids and pre-existing syngenetic/diagenetic pyrite for both the carbonate- and arenite-hosted deposits.     

Gold recovery from a refractory pyrrhotite ore by biooxidation

The aim of the present investigation was to study the biooxidation of a refractory gold-bearing pyrrhotite, in order to increase the gold recovery during the subsequent conventional cyanidation.Bacterial cultures utilised in the biological test consisted predominantly of Thiobacillus genus. Tests were conducted at laboratory scale. The gold content of the ore sample, coming from Bolivia, was of 10 g t⁻¹ Au.After 24 h leaching time by direct cyanidation, low gold recovery was obtained (<20% Au), with a high reagent consumption. On the other hand, a high gold recovery was achieved for the biooxidated samples: after 24 h cyanidation gold dissolution reached about 91% Au.Experimental results have shown the technical feasibility of the biooxidative pretreatment prior to conventional leaching and a complete circuit of treatment, on laboratory scale, has been developed considering also the subsequent gold recovery by carbon adsorption/desorption and electrowinning.A gold extraction yield of about 86% was determined in the whole process for gold extraction from pyrrhotite (biooxidation, solid–liquid separation, cyanidation, adsorption, desorption, electrowinning).