Leaching and differential recrystallization of metamict zircon under experimental hydrothermal conditions

We report results of hydrothermal experiments on four alluvial zircons from Sri Lanka, which cover a wide range of radiation damage, at 450 °C and 1.3 kbar for 744 h with 2 M CaCl₂ solution as reactive fluid. After the hydrothermal treatment, the most metamict samples show micrometer-thick reaction rims, which surround apparently unreacted zircon, as revealed by cathodoluminescence (CL) and Nomarski differential interference contrast (NDIC) images. These rims have sharp, curved, and transgressive boundaries with unreacted zircon and are, in some cases, spread out along cracks. The thickness of reaction rims increases with increasing cumulated !-dosage of the starting materials. The reaction rims are strongly enriched in Ca (up to 7000 ppm) and a water species and depleted in radiogenic Pb, Zr, and Si, as revealed by electron microprobe analyses. A significant Th loss from the reaction rims was detected in the case of the most metamict sample, whereas U remained in the structure. FT-infrared spectrometry and X-ray diffraction measurements revealed that the bulk run products were recrystallized. Using micro-Raman spectrometry, we were able to demonstrate that differential recrystallization took place. The reaction rims are strongly recrystallized, whereas the unreacted grain interiors underwent only minor recrystallization. Recrystallization of the rims is accompanied by an enhancement of the integral CL intensity. It is suggested that recrystallization in the reaction rims was catalyzed by water infiltration and ion exchange and prevented significant congruent zircon dissolution under the given experimental conditions. Previous zircon studies have shown that (1) a transgressive morphology, (2) a reduced Th-U ratio, and (3) an enhanced CL emission are also characteristics of rims in zircons from high-grade metamorphic rocks. Based on these similarities between natural and experimentally produced rims, it is suggested that leaching-catalyzed recrystallization is an important alteration process in zircon under wet geological conditions and can account for many complex core-rim structures found in natural zircons. Furthermore, the strong enrichment of Ca in the reaction rims supports previous assumptions that high Ca concentrations in natural zircons are of secondary origin. It is suggested that lower U-Pb concordia intercept ages obtained from single-phase zircons with high Ca contents date a leaching event.     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Experimental modelling of corona textures

Formation of corona textures along olivine–plagioclase and orthopyroxene–plagioclase interfaces has been experimentally reproduced at 670 and 700 °C and 5 kbar with either a pure H₂O fluid phase or 0.1 and 37 m NaCl–H₂O solution fluid. In these experiments, we investigate the interaction of primary olivine and/or orthopyroxene and plagioclase in powders and polished crystals, and in small samples of a natural gabbro. The experiments result in the formation of corona textures with several layers of different assemblages (according to the experimental conditions) consisting of garnet (grossular), clinopyroxene, orthopyroxene, amphibole, chlorite and phlogopite. The experiments show major differences in the number of layers, the mineral assemblages and mineral composition, and in the trends of composition of plagioclase in coronas around olivine and orthopyroxene. The fluid phase composition influences the corona assemblages and the composition of the minerals in the experimental coronas; for example, garnet appears in the coronas in the second experiment where the NaCl–H₂O ratio is low. Experimental modelling of corona textures confirms a model of simultaneous growth of layers by the mechanism of diffusion metasomatism with participation of a fluid phase through which mass is transferred. Zoning in the experimental coronas shows opposing diffusion of Al and Ca from plagioclase and Mg and Fe from olivine/orthopyroxene; difference in the mobility of the components is inferred from observations in the coronas. The experimental corona textures are compared with natural coronas from the Belomorian belt (Baltic shield), developed at 670–690 °C and 7–8 kbar, and the Marun‐Keu complex (Polar Urals), developed at 670–700 °C and 14–16 kbar, where the corona textures correspond to a transitional stage of the gabbro‐to‐eclogite transformation.     

Metamorphic evolution of garnet-bearing ultramafic rocks from the Gongen area, Sanbagawa belt, Japan

Garnet‐bearing ultramafic rocks including clinopyroxenite, wehrlite and websterite locally crop out in the Higashi‐akaishi peridotite of the Besshi region in the Cretaceous Sanbagawa metamorphic belt. These rock types occur within dunite as lenses, boudins or layers with a thickness ranging from a few centimetres to 1 metre. The wide and systematic variation of bulk‐rock composition and the overall layered structure imply that the ultramafic complex originated as a cumulate sequence. Garnet and other major silicates contain rare inclusions of edenitic amphibole, chlorite and magnetite, implying equilibrium at relatively low P–T conditions during prograde metamorphism. Orthopyroxene coexisting with garnet shows bell‐shaped Al zoning with a continuous decrease of Al from the core towards the rim, consistent with rims recording peak metamorphic conditions. Estimated P–T conditions using core and rim compositions of orthopyroxene are 1.5–2.4 GPa/700–800 °C and 2.9–3.8 GPa/700–810 °C, respectively, implying a high P/T gradient (> 3.1 GPa/100 °C) during prograde metamorphism. The presence of relatively low P–T conditions at an early stage of metamorphism and the steep P/T gradient together trace a concave upwards P–T path that shows increasing P/T with higher T, similar to P–T paths reported from other UHP metamorphic terranes. These results suggest either (1) down dragging of hydrated mantle cumulate parallel to the slab–wedge interface in the subduction zone by mechanical coupling with the subducting slab or (2) ocean floor metamorphism and/or serpentinization at early stage of subduction of oceanic lithosphere and ensuing HP–UHP prograde metamorphism.     

Magmatic zoning in apatite: a monitor of porosity and permeability change in granites

Apatites from the Shap Granite, northern England, are strongly zoned, reflecting multiple generations of growth and dissolution. Such chemical zoning is most readily displayed in cathodoluminescence images and correlates well with trace element variation determined using LA-ICP-MS analyses. The zoned apatites provide a detailed record of the changing scales of permeability during progressive crystallisation within the magma chamber. Early periods of apatite growth are preserved within cores and represent both early growth within a magma chamber dominated by vigorous mixing processes and inherited grains with significantly different chemistries. The main phase of apatite growth within the magma was strongly controlled by the presence of adjacent biotite phenocrysts and is characterised by fine scale oscillatory zoning, followed by the growth of a thin rim of relatively uniform composition. The chemical evolution of the later phases of apatite growth and the stratigraphy of the zoning appear to record late stage crystallisation within progressively more isolated interstitial melt pockets.Editorial responsibility: I. Parsons     

Particle size distribution and dissolution properties of metals in cyclone fly ash

The particles in the examined cyclone fly ash were all smaller than 0.25 mm. in diameter, and particles smaller than 0.075 mm. in diameter accounted for 88.4 % of the ash weight. This result indicates that cyclone fly ash consists of particles with a small diameter. The metals in the cyclone fly ash were enriched in small particles. The highest concentrations for zinc, copper, lead, cadmium and molybdenum in the cyclone fly ash were found in the smallest particle size fraction (< 0.075 mm.) and for Barium, chromium, nickel, Vanadium and Cobalt in the second to smallest particle size fraction (0.075-0.125 mm.). From an environmental and toxicological standpoint, the smallest particles are of the greatest concern when ash is handed at landfill disposal sites (transport and disposal especially in stormy weather conditions), and some studies have reported risks to workers from prolonged exposure to ash. The results of the comparison of various dissolution methods for metals showed that the digestion procedures with nitric acid alone (USEPA 3051) or with a mixture of nitric acid + hydrogen peroxide (USEPA 3050B) slightly underestimated the metal concentrations in the cyclone fly ash. Although the use of hydrofluoric acid is often necessary for the determination of a number of elements associated with siliceous minerals, its use can result in loss of trace elements during dissolution.     

SHRIMP zircon dating and Nd isotopic systematics of Palaeoproterozoic migmatitic orthogneisses in the Epupa Metamorphic Complex of northwestern Namibia

The Epupa Metamorphic Complex constitutes the southwestern margin of the Congo Craton and is exposed in a hilly to mountainous terrain of northwestern Namibia, bordering the Kunene River and extending into southern Angola. It consists predominantly of granitoid gneisses which are migmatized over large areas. This migmatization locally led to anatexis and produced crustal-melt granites such as the Otjitanda Granite. We have undertaken reconnaissance geochemical studies and single zircon U–Pb SHRIMP and Pb–Pb evaporation dating of rocks of the Epupa Complex. The granitoid gneisses, migmatites and anatectic melts are similar in composition and constitute a suite of metaluminous to peraluminous, calc-alkaline granitoids, predominantly with volcanic arc geochemical signatures. The zircon protolith ages for the orthogneisses range from 1861 ± 3 to 1758 ± 3 Ma. Anatexis in the migmatitic Epupa gneisses was dated from a melt patch at 1762 ± 4 Ma, and the anatectic Otjitanda Granite has a zircon age of 1757 ± 4 Ma. Migmatization and anatexis therefore occurred almost immediately after granitoid emplacement and date a widespread high-temperature Palaeoproterozoic event at ∼1760 Ma which has not been recorded elswhere in northern Namibia. The Nd isotopic systematics of all dated samples are surprisingly similar and suggest formation of the protolith from a source region that probably separated from the depleted mantle about 2.4–2.0 Ga ago. A major Archaean component in the source area is unlikely.     

The Catoca kimberlite pipe, Republic of Angola: A paleovolcanological model

The Catoca kimberlite pipe is among the world’s largest primary diamond deposits. The Catoca volcanic edifice is only slightly eroded. Kimberlitic rocks of various facies compose a crater of about 1 km in diameter and a diatreme. The structure of the pipe and mining conditions of the deposit are complicated by intense intrapipe tectonic processes related to large-amplitude subsidence. Based on geological data, we propose a structural model of the deposit and a paleovolcanological model of the Catoca pipe formed during a full cycle beginning with a stage of active volcanism and completed by stages of gradually waning volcanic activity and sedimentation. It is suggested that the banded tuffisitic kimberlite of the crater zone was deposited at the stage of active volcanic eruption from specific pyroclastic suspension as a low-viscosity mixture of crystals and aqueous sol rich in serpentine.     

A comparison of the properties and salt weathering susceptibility of natural and reconstituted stones of the Orval Abbey (Belgium)

The Orval Abbey, a major monument of southern Wallonia, Belgium, was partly destroyed and rebuilt several times between the Middle Ages and the present time. The oldest parts are made of natural stones of local origin (Bajocian and Sinemurian limestones) and the most recent parts are mostly made of reconstituted stone. The process of reconstituted stone making is not known. Although confronting the same environmental conditions, the reconstituted stone is much more susceptible to weathering than the natural limestones, especially to salt crystallisation. The present study compared the mineralogical and petrophysical properties of these building materials to gather information on the making of the reconstituted stone and to understand the difference in salt susceptibility between natural and reconstituted stones. Microscopic observations and petrophysical measurements showed that the reconstituted stone is composed of debris of Sinemurian and Bajocian limestone and cement, and the salt efflorescences were thenardite. Within the cement, amorphous grains were found that may correspond to grains of clinker, which have not reacted during stone making. Although its porosity and water transfer properties were close to that of the Bajocian limestone, its pore access distribution was centred around 0.1 μm. Furthermore, the details of the pore size distribution allowed calculating salt susceptibility indices that were very high in the case of the reconstituted stone. Thus, the composition of the cement and the pore size distribution are likely the two factors explaining a high susceptibility of the reconstituted stone to salt weathering.