Secondary Alteration Products Research Articles

Rare Earth Element Behaviour During Evolution and Alteration of the Dartmoor Granite, SW England

The distribution of rare earth elements (REE) within the compositionally zoned Dartmoor pluton is used to constrain models of granite evolution and to assess the effects of pervasive hydrothermal alteration on REE mobility. The main process of magma evolution was crystal fractionation of early plagioclase, biotite, and accessory minerals (apatite, monazite, zircon, and xenotime). Concentrations of REE (particularly LREE and Eu) and other elements (Fe2O3t, MgO, CaO, TiO2, Zr, Ba, and Sr) decrease strongly with evolution of the pluton from 71 to 74% SiO2. These trends, and the inward zoning of the pluton, are compatible with differentiation by crystal fractionation at the level of emplacement, a process that gave rise to a marginal cumulate granite (CGM) modified by country rock assimilation, a body of inner granite (PM), and a late-stage evolved granite (FG) that intruded the earlier types. REE modelling of the Dartmoor granite types by fractional crystallization of REE-enriched accessory minerals from a parent PM-granite shows that the FG-granite cannot have formed from a residual liquid left by crystallizati on of the CGM-granite. Two discrete stages of crystallization occurred; side-wall cumulate CGM-granite crystallization dominated by LREE-enriched monazite fractionation followed by a late-stage mobile residual FG-granite in which fractionation was dominated by HREE-enriched apatite and zircon. Modelling supports the idea that largescale assimilation of country rock was not the dominant process during Dartmoor granite evolution. Pervasive hydrothermal alteration locally affected all Dartmoor granite types, altering primary plagioclase, biotite, apatite, monazite, and, to a lesser extent, zircon and xenotime. During pervasive sericitization, chloritization, and tourmalinization, REE were mobilized over distances of centimetres only and redistributed into the secondary alteration products seridte, chlorite, tourmaline, allanite, and sphene. Whole-rock REE abundances were not affected

Na‐bearing Ca‐Al‐rich inclusions in the Yamato‐791717 CO carbonaceous chondrite

Abstract Ca‐Al‐rich inclusions (CAIs) in the Yamato‐791717 CO carbonaceous chondrite contain 5 to 80 vol% of nepheline, along with minor sodalite, and thus are among the most nepheline‐rich CAIs known. The primary phases in inclusions are mainly spinel, fassaite, aluminous diopside, perovskite, and hibonite. In contrast to many CO chondrites, melilite is rare. Spinel contains variable amounts of Fe (0 to 57 mol% FeAl2O4) and is commonly zoned. Texture suggests that nepheline is a secondary alteration product formed by replacing mainly melilite, fassaite, and spinel; melilite is the most susceptible to alteration of the primary phases, so most of it was probably already consumed to form nepheline. The majority of inclusions are single concentric objects or aggregates of concentric objects. Lightly altered inclusions have cores of spinel surrounded by bands of nepheline (replacing fassaite), fassaite, and diopside. In moderately altered inclusions, spinel cores are replaced by nepheline. In heavily altered inclusions, the major part of internal areas (50 to 80% in volume) are replaced by nepheline. In some moderately and heavily altered inclusions, only diopside rims remain unaltered. Textural relationships indicate that the resistance of primary phases to alteration increases in the order melilite, fassaite, spinel, diopside. The alteration probably proceeded with reaction of the primary phases with the low‐temperature (≤ 1000 K) nebular gas rich in Na, Fe and CI. The degree of alteration in Y791717 CAIs appears to be much higher than those in CAIs in other reported meteorites.

Chemical compositions of refractory inclusions from the Vigarano and Leoville carbonaceous chondrites

Major and trace elements were determined by INAA in two hibonite-rich refractory inclusions and a dark clast from Vigarano, three refractory inclusions from Leoville, and a hibonite-rich and a melilite-rich fraction from a composite refractory inclusion from Allende. The refractory inclusions from Vigarano and Leoville are all similar to their counterparts in Allende in that they have groups I, II, and III refractory element fractionation patterns, but a large proportion of these Vigarano and Leoville inclusions also contain refractory element features that are very infrequently encountered in Allende inclusions. For example, Vigarano 1623-2 is a group I inclusion with a large Ce anomaly ( La Ce = 2.34 ± 0.32 relative to Cl); Vigarano 1623-3 is a group III in which Os is strongly fractionated relative to other refractory siderophiles ( Os Re = 2.13 ± 0.08 relative to Cl); and Leoville 3537-1 is a modified group II in which removal of refractory REEs and condensation of the remaining REEs both occurred at unusually low temperatures. All samples from Vigarano and Leoville, including a fine-grained inclusion, have Na, Au, and other volatile element concentrations at or below the low end of the concentration ranges for these elements in Allende coarse-grained inclusions. This is consistent with the much lower amounts of Na-rich, secondary alteration products in the Vigarano and Leoville inclusions than in the ones from Allende. Even the Vigarano dark clast has a lower Na content than Allende dark clasts. Secondary alteration of refractory inclusions in the reduced subgroup of C3 V meteorites occurred in a part of the solar nebula where grain-gas separation processes removed the inclusions from chemical communication with the gas at a higher temperature or after a shorter time than in the case of Allende inclusions. The hibonite- and melilite-rich parts of the Allende inclusion could have formed in separate parts of the same chemical reservoir by separation of early condensing hibonite from melilite. The relatively hibonite-rich Vigarano inclusions may have accumulated originally from condensates preferentially enriched in hibonite by gravitational settling of grains of this early condensate or by their transport in convection cells.

Constraints by Experimental Data for Modeling of Radionuclide Release from Spent Fuel

ABSTRACTComparison of spent fuel corrosion data from nuclear waste management projects in Canada, Sweden and the USA strongly suggests that the release of 90Sr to the leachant can be used as a measure of the degradation (oxidation/dissolution) of the fuel matrix. A surprisingly quantitative similarity in the 90 Sr release data for fuel of various types (BWR, PWR, Candu), linear power ratings and burnups leached under oxic conditions was observed in the comparison. After 1000 days of leachant contact, static or sequential, the fractional release rates for 90Sr (and for cesium nuclides) were of the order of 10−7/d.The rate of spent fuel degradation (alteration) under oxic conditions can be considered to be controlled either by the growth rates of secondary alteration products, by oxygen diffusion through a product layer, by the rate of formation of radiolytic oxidants or by solubility-controlled dissolution of the matrix. These processes are discussed. Methods for determining upper limits for long-term 90Sr release, and hence fuel degradation, have been derived from the experimental data and consideration of radiolytic oxidant production.

Alteration of Al-rich inclusions inside amoeboid olivine aggregates in the Allende meteorite

Lightly altered Al-rich inclusions in amoeboid olivine aggregates have cores containing primary melilite + fassaite + spinel + perovskite and no secondary alteration products. In moderately altered inclusions, whose cores now contain only fassaite + spinel + perovskite, melilite was replaced by a fine-grained mixture of grossular + anorthite + feldspathoids and perovskite was partially replaced by ilmenite. In heavily altered inclusions, fassaite has been replaced by a mixture of phyllosilicates + ilmenite and the remaining primary phases are spinel ± perovskite. In very heavily altered inclusions, no primary phases remain, the spinel having reacted to form either phyllosilicates or a mixture of olivine + feldspathoids. This sequence of alteration reactions may reflect successively lower solar nebular equilibration temperatures. During alteration, SiO 2, Na 2O, K 2O, FeO, Cr 2O 3, H 2O and Cl were introduced into the inclusions and CaO was lost. MgO may have been lost during the melilite reaction and added during formation of phyllosilicates. Electron microprobe analyses indicate that the phyllosilicates are a mixture of Na-rich phlogopite and chlorite or Alrich serpentine. Thermodynamic calculations suggest that, at a solar nebular water fugacity of 10 −6, Na-rich phlogopite could have formed from fassaite at ~470 K and chlorite from Na-rich phlogopite at ~328 K. Olivine mantling Al-rich inclusions is not serpentinized, suggesting that these objects stopped equilibrating with the nebular gas above 274 K.

Fluid flow and mineral reactions at high temperatures and pressures

Although fluid flows in response to differences in hydraulic head, chemical reactions occur in response to changes in fluid pressure. Depending on the flow direction, cross-sectional area, and hydraulic conductivity of the system, flow of fluids through porous media may lead to increases and/or decreases in fluid pressure along the flow path. At high temperatures corresponding to those in the supercritical region of the system H 2 O, mass transfer among minerals and aqueous fluids in hydrothermal systems is sensitive to changes in fluid pressure as well as temperature. As a consequence, mineral solubilities may both increase and decrease in the direction of fluid flow, causing development of isolated channelways and a heterogeneous distribution of secondary porosity and alteration products. For example, vertical downward flow is accompanied by increasing fluid pressure if the Darcy velocity is less than the hydraulic conductivity of the medium. Hence, for a constant flow rate an abrupt increase in cross-sectional area may lead to dissolution of quartz, but precipitation of sulphides.

“Fluffy” Type A Ca-, Al-rich inclusions in the Allende meteorite

Allende “fluffy” Type A's (FTA's) are a distinct sub-group of Ca-, Al-rich inclusions whose primary mineral assemblage consists of Al-rich melilite (Åk 0–33), spinel that is commonly very V-rich, perovskite and, frequently, hibonite. Some contain relatively coarse-grained melilite (up to 1.5 mm) that is intensely kink-banded and commonly reversely-zoned, hibonite and V-rich spinel. Others contain much finer-grained and strain-free melilite (≲50 μm) and have not been found to contain hibonite or V-rich spinel. Some FTA's contain both coarser- and finer-grained melilite and textural relationships indicate that the latter is replacing the former. FTA's are characterized by extremely irregular shapes and 60–75 volume per cent of fine-grained, secondary alteration products. Many are aggregates of innumerable nodules, each of which is surrounded by a Wark-Lovering-type rim sequence. These nodules are frequently separated from one another by matrix-like clastic rim material. Other FTA's do not have nodular structure. Structural and mineralogical characteristics of their Wark-Lovering rims suggest that FTA's did not achieve their shapes by deformation of a liquid or a hot, plastic solid. In contrast to those in Type B inclusions, formation of reverse zoning in the coarser-grained melilite crystals in FTA's cannot be understood in terms of crystallization from a liquid but are readily explainable by condensation from a solar nebular gas during a period of falling pressure. Further evidence against a liquid origin is the wide range of spinel compositions within individual coarser-grained FTA's. The fact that the reversely-zoned melilite crystals cannot have been produced in any kind of sublimation or distillation process precludes formation of these inclusions as volatilization residues. FTA's are aggregates in some of which are preserved vapor-solid condensate grains that formed at high temperature in the solar nebula.

The chemical and isotopic record of rock-water interaction in the Sherman Granite, Wyoming and Colorado

Chemical, isotopic, radiographic, and rock-leaching data are combined to describe the effects of rock-water interactions in core samples of petrographically fresh, 1.43 b.y.-old Sherman Granite. The data serve to identify sensitive indicators of incipient alteration and to estimate the degree, pathways, and timing of element mobilization. Unfractured core samples of Sherman Granite are remarkably fresh by most chemical or isotopic criteria, but incipient alteration is indicated by the abundance and distribution of uranium and the degree of radioactive equilibration of uranium with its decay products. Uranium abundances which are out of equilibrium with lead decay products indicate remobilization of a portion (3 to 60 percent) of original uranium in late Phanerozoic time. Association of uranium with minor but pervasive secondary alteration products also indicates some remobilization. The amount of apparent uranium mobility in unfractured Sherman Granite (3 to 60 percent) is small compared to the results of similar studies of Archean granites from nearby localities. Chemical and isotopic data evaluated as a function of core-sample depth suggest a uranium migrational pathway involving near-surface leaching and reconcentration at depth. Movement of solutions through the upper 200 ft (60 m) of Sherman Granite is fracture controlled, and brecciated granite shows more obvious petrographic, chemical, and isotopic evidence of alteration and multi-element redistribution. Laboratory experiments using freshly crushed Sherman Granite confirm that uranium is leached in preference to elements such as Si, Mg, Ca, and K, and that leachable uranium is situated close to the solid-liquid interface; perhaps as uranium along grain boundaries, in crystal defects, or on cleavage traces of minerals that exclude uranium from their structure.

Thermochemical remanent magnetization in Jurassic silicic volcanics from Nevada, U.S.A.

Characteristic magnetizations from Middle Jurassic dacitic to andesitic subaerial volcanics (the Fulstone and Artesia Formations) in the Buckskin Mountain Range, western central Basin and Range Province, are well-grouped, generally display univectorial decays to the origin in demagnetization and have hematite blocking temperatures restricted almost entirely to above 620°C. Petrographic, rock magnetic and electron microprobe investigations confirm that nearly pure hematite is the essential magnetic phase (up to about 10 vol. %) occurring as a replacement of coarse titaniferous magnetite phenocrysts and fine groundmass particles, as a secondary alteration product of ferromagnesian phenocrysts and as a mobilized phase filling cracks and other open spaces. The presence of antipodal directions in each flow unit and in interbedded volcanoclastic units (some having retained magnetite as a major magnetic phase) and magnetite-dominated remanences in time-equivalent intrusives cutting the flows indicates that the volcanics acquired their hematite remanence, a faithful record of the geomagnetic field, in high-temperature, deuteric oxidation during and following their emplacement, not during a later thermal event such as regional metamorphism. The remanence is probably a thermochemical remanent magnetization, although part may be of thermoremanent origin.

X-ray diffraction and magnetic studies of altered ilmenite and pseudorutile

SynopsisIT was not until 1966 that pseudorutile was first defined. Earlier, its X-ray diffraction spectrum had been confused with that of futile and, to a lesser degree, with those of hematite and ilmenite. Subsequent work has shown that pseudorutile has a world-wide distribution in detrital ilmenite-bearing heavy mineral deposits. The present work has confirmed its magnetic susceptibility and density. In addition pseudorutile is shown to be a magnetic spin glass with a peak susceptibility at 23 °K.Altered ilmenites, in which pseudorutile occurs as a secondary alteration product, display a range of chemical composition and magnetic susceptibility. The most highly magnetic fractions are not necessarily those containing the least-altered ilmenite, and in material from Capel, Western Australia, the most highly magnetic fractions were those containing grains of ferrimagnetic ferrian ilmenite.Quantitative X-ray diffraction has shown that West Australian altered ilmenite contains significant amounts of amorphous ilmenite, pseudorutile, and rutile. The magnetic susceptibility of paramagnetic fractions of altered ilmenite from Capel, Western Australia, can be calculated from normative compositions based on chemical analyses.

Mars surface composition from reflectance spectroscopy: A summary

Visible and near‐infrared (0.3–2.6 μm) reflectance spectra of the martian surface have been obtained primarily from earth‐based telescopic observations, and multispectral images have been obtained both from spacecraft and earth‐based observations. Observations in this wavelength region have confirmed the bimodal albedo distribution of surface materials, first observed visually. All spectra of Mars are characterized by strong Fe3+ absorptions from the near‐UV to about 0.75 μm. Darker regions show this effect to a lesser degree, and are interpreted to be less oxidized materials. In addition, dark areas have Fe2+ absorptions near 1.0 μm, attributed primarily to olivines and pyroxenes. There is evidence at infrared wave‐lengths for highly dessicated mineral hydrates and for H2O‐ice and/or adsorbed H2O. Observations of the north polar cap show a strong H2O‐ice spectral signature but no spectral evidence for CO2‐ice, while only CO2‐ice has been identified in spectra of the south polar cap. While the brightest materials on Mars are widespread and correlate with aeolian dust, darker materials show greater mineralogic variability and are thought to be closer in petrology and physical location to their parent rock. At present the best model for the dark materials is somewhat oxidized basaltic or ultramafic rock, regionally variable in composition and details of oxidation. The bright materials appear to be finer‐grained assemblages of primarily highly oxygen‐sharing dessicated mineral hydrate, some ferric oxides, and other less major constituents, including a small amount of relatively unaltered mafic material. The bright materials seem likely to be primary and/or secondary alteration products of the basaltic or ultramafic dark materials.

Primodial retention of carbon by the terrestrial planets

Chemical equilibrium calculations on the stability of pure and dissolved graphite and cohenite (Fe 3C), several other carbides, and several carbonates have been carried out for a system with solar elemental abundances over a very wide range of temperature and pressure. The calculated abundances of condensed carbon compounds are similar to the observed inventories on Earth and Venus, but fully 10 times smaller than the minimum carbon abundance found in ordinary chondrites. The total carbon content of most iron meteorites is compatible with their origin as a cooling FeNiCSP solution which was saturated with dissolved carbon at the solidus, such as would be produced by melting an ordinary chondrite, not by direct condensation from or equilibrium with the primitive solar nebula. It is argued that the carbon content of Mars need not be appreciably greater than that of the Earth. Material with even lower formation temperatures than Mars, such as the primitive material in the asteroid belt, may retain substantially more carbon as disequilibrium polymeric organic matter, possibly by the Fischer-Tropsch mechanism favored by Anders. Carbonates are not found as equilibrium products in a solar-composition system, and are probably secondary alteration products. CaCO 3 might, however, persist in a solar-composition gas at temperatures below 460°K and pressures below 10 −6.6 bar. The most stable condensed carbon compounds are found to be graphite, Fe 3C, and possibly TiC, all in solid solution in the metal phase.

Chemical and optical studies of glass shards in Pleistocene and Pliocene ash layers from DSDP site 192, Northwest Pacific Ocean

Thirty-four ash layers of Pleistocene and Pliocene age from DSDP Site 192, northwestern Pacific Ocean, have been subjected to detailed chemical and optical study to evaluate: (1) the chemical and optical variability in glass shards from deep-sea ash layers, and (2) secondary changes brought about by prolonged exposure to seawater. Glass shards from approximately half of the ash layers studied were found to have uniform compositions which approach the precision of the microprobe chemical analyses, whereas the remainder are compositionally diverse (e.g., SiO 2, variations of 5–15% among shards from the same ash layer) and appear to be the eruptive products of compositionally zoned magma chambers. Optical studies of glass shards confirm the absence of devitrification or the formation of pervasive secondary alteration products. By contrast, chemical studies suggest that the glass shards have experienced progressive hydration with possible minor ion exchange of K, Mg, Ca and Si. The hydration occurs rapidly and leads to a rather uniform water content of 4.5–5% after several hundred thousands of years exposure to seawater. Step-wise heating dehydration experiments, optical effects, and published'oxygen isotope studies indicate that the water of hydration is incorporated uniformly within the glass. Systematic chemical differences between electron microprobe analyses of glass shard interiors and corresponding bulk chemical study by atomic absorption lead us to postulate that glass shard margins have undergone a minor chemical exchange with major cations in seawater. They have gained 0.10–0.20 wt. % K 20, MgO, and CaO while losing a corresponding amount of Si 2O. Although the glass shards from DSDP Site 192 are hydrated and may have experienced subtle, surficial ion exchange, we stress that they are the most chemically representative samples available of magmas that were explosively erupted from volcanic arcs.

Base metal enrichment in volcanic sublimates and secondary alteration products from Vesuvius and Vulcano

SummaryA wide range of volcanic sublimates and alteration products from the Johnston-Lavis collection has been analysed for major elements plus copper, lead, and zinc. 'Aphthitalite' and 'natrikalite' from Mount Vesuvius and an 'alum' from the island of Vulcano all proved to be enriched in copper and selected analyses are tabulated. The process leading to copper and lead enrichment of the Vesuvian material may be vapour phase transport as chloride followed by sulphation on sublimation. It is suggested that the source of the copper found in the alum sample from Vulcano could be of interest to economic geologists.

A List of Minerals Found in Riley County Kimberlites

More than fifty distinct minerals have been identified in the kimberlite pipes of Riley County, Kansas by x-ray, optical, and chemical methods; and the presence of approximately twenty more is indicated. Primary kimberlite minerals constitute only a small percentage of those found as most occur in xenoliths and as secondary alteration and/or replacement products.