Studies in clay chemistry

A study of clay chemistry has been approached with three aims: - to modify the conducting properties by intercalation of tetrathiafulvalene, - to study the electrochemistry of redox-active coordination compounds immobilised on clay coated electrodes, and - to study the role of clays as reagents in inorganic glass forming reactions using mainly solid-state magic-angle-spinning NMR. TTF was intercalated by smectites containing different interlayer and lattice cations. Evidence from ESR and 57Fe Mossbauer indicated charge-transfer from TTF to structural iron in natural montmorillonite, and to interlayer Cu2+ in Cu2+ exchanged laponite. No charge transfer was observed for laponite (Na+ form) itself. Ion exchange of TTF3(BF4)2 with laponite was found to proceed quantitatively. The intercalated species were believed to be (TTF)2+ dimers. Conductivity data showed an order of magnitude increase for the intercalated clays. The mechanism is thought to be ionic rather than CT as Na+ laponite showed a similar enhancement in conductivity. Mechanically robust colloidal clay films were prepared on platinum electrodes. After immersion in solutions containing redox active complexes [Co(bpy)3]3+ and [Cr(bpy)3]3+, the films became electroactive when a potential was applied. Cyclic voltammograms obtained for both complexes were found to be of the diffusion controlled type. For [Co(bpy)3]3+ immobilised on clay coated electrodes, a one-step oxidation and four-step reduction wave was observed corresponding to a one electron stepwise reversible reduction of Co(III), through Co(II), Co(I), Co(O) to Co(I) oxidation state. For [Cr(bpy)3]3+ the electrochemistry was complicated by the presence of additional waves corresponding to the dissociation of [Cr(bpy)3]3+ into the diaquo complex. ESR and diffuse reflectance data supported such a mechanism. 29Si, 27Al and 23Na MAS NMR spectroscopy, supported by powder XRD and FTIR, was used to probe the role of clays as reagents in glass forming reactions. 29Si MAS NMR was found to be a very sensitive technique for identifying the presence and relative abundance of crystalline and non-crystalline phases. In thermal reactions of laponite formation of new mineral phases such as forsterite, akermanite, sillimanite and diopside were detected. The relative abundance of each phase was dependent on thermal history, chemical nature and concentration of the modifier oxide present. In continuing work, the effect of selected oxides on the glass forming reactions of a model feldspar composition was investigated using solid state NMR alone. Addition of network modifying oxides generally produced less negative 29Si chemical shifts and larger linewidths corresponding to a wider distribution of Si-O-Si bond angles and lengths, and a dominant aluminosilicate phase with a less polymerised structure than the starting material. 29Si linewidths and 27Al chemical shifts were respectively correlated with cationic potential and Lewis acidity of the oxide cations. Anomalous Al(4) chemical shifts were thought to be due to precipitation of aluminate phases rather than a breakdown in Lowenstein's aluminium avoidance principle.

The metamorphic environments of the Strontian, Foyers and Dalbeattie intrusions, Scotland

Three metamorphic aureoles around intrusions of the Caledonian 'Newer Granite' suite are described. Each represents a different orogenic environment. The Strontian complex is intruded into sillimanite grade Moinian metasediments at the core of the orogen. The aureole comprises three zones; a transitional muscovite + sillimanite + K-feldspar zone, a sillimanite + K-feldspar zone and an inner cordierite + K-feldspar zone. Contact migmatization occurs in the inner part of the aureole. Zoning profiles from garnets in both regional and aureole assemblages show retrograde Mn-rich rims. Fe and Mg compositions are re-equilibrated to contact conditions. Apparent re-equilibration of Ca compositions results from increasingly ideal solid solution behaviour of Ca in plagioclase and garnet with increasing temperature. Temperatures of 690°C at 4.1 kbar (XH2O = 0.53) are estimated in the cordierite + K-feldspar zone, dropping to 630°C (XH2O = 0.69) at the sillimanite + K-feldspar isograd. The zones increase in width to the east, influenced by the regional thermal gradient at the time of intrusion. The timer-scale of the contact event, t2, relative to the regional, tl, - is estimated as t2/t1 = 101.1+ -0.7 and is consistent with Intrusion at an early stage of regional uplift and cooling. The Foyers complex intrudes Moinian rocks at a higher structural level. Regional assemblages range from garnet to sillimanite grade. Three contact zones are recognised; a sillimanite zone, a sillimanite + K-feldspar zone and an inner cordierite + K-feldspar zone. The limit of the aureole is marked by the breakdown of garnet which shows disequilibrium, both texturally, and in complex zoning profiles, within it. Temperatures of 660°C at 3.9 kbar (XH20 = 0.14) are estimated in the cordierite + K-feldspar zone? The Dalbeattie complex is at the margin of the orogen, intruded into low grade Silurian metasediments. Two zones are recognised; a biotite zone and an inner hornblende zone. Cordierite and diopside are present in the inner zone.

Petrologia do Plutão Bom Jardim de Goiás (PBJG): implicação na evolução neoproterozoica da Província Tocantins

The Bom Jardim de Goiás Pluton (PBJG) is a semi-circular body, located in the central portion of the Tocantins Province, intrusive into orthogneisses and metassupracrustals of the Arenópolis Magmatic Arc. These metasupracrustals present a low to moderate dipping banding or schistosity, have a low to moderate angle of banding / foliation, defined by mica, andalusite and sillimanite and cordierite, which characterize an amphibolite facies metamorphism. This structure is crosscut by the emplacement of the PBJG rocks. The abrupt nature of the contacts and the absence of ductile structures indicate that the intrusion took place in a relatively cold crust. Under petrographic grounds, the pluton consists mainly of monzodiorites, tonalite and granodiorite, following the low to medium-K calk-alkaline alkaline trend. Rocks of the PBJG have hornblende and biotite as the main mafic phases, besides subordinate clinopyroxene, titanite, epidote and opaque. Late dikes of leucogranite contain only mineral biotite as relevant accessory mineral. One U-Pb zircon dating of a monzodiorite yielded an age of 550 ± 12 Ma (MSWD = 1.06). Whole-rock and mineral chemistry suggest that the studied rocks are calc-alkaline, having evolved by fractional crystallization of Ca- and Fe-Mg minerals under high oxygen fugacity. Using the amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer, we calculate temperatures and pressures of, respectively, 692-791 °C e 2.4-5.0 kbar for the intrusion of the PBJG, which is corroborated by previous metamorphic assemblages in the country rocks. The geological, geochemical and geochronological features of PBJG demonstrate their post-tectonic or post-collisional nature, with emplacement into an already uplifted and relatively cool crust at the end of brasiliano orogeny in this portion of the Tocantins Province.

Petrologia do Plutão Bom Jardim de Goiás (PBJG): implicação na evolução neoproterozoica da Província Tocantins

The Bom Jardim de Goiás Pluton (PBJG) is a semi-circular body, located in the central portion of the Tocantins Province, intrusive into orthogneisses and metassupracrustals of the Arenópolis Magmatic Arc. These metasupracrustals present a low to moderate dipping banding or schistosity, have a low to moderate angle of banding / foliation, defined by mica, andalusite and sillimanite and cordierite, which characterize an amphibolite facies metamorphism. This structure is crosscut by the emplacement of the PBJG rocks. The abrupt nature of the contacts and the absence of ductile structures indicate that the intrusion took place in a relatively cold crust. Under petrographic grounds, the pluton consists mainly of monzodiorites, tonalite and granodiorite, following the low to medium-K calk-alkaline alkaline trend. Rocks of the PBJG have hornblende and biotite as the main mafic phases, besides subordinate clinopyroxene, titanite, epidote and opaque. Late dikes of leucogranite contain only mineral biotite as relevant accessory mineral. One U-Pb zircon dating of a monzodiorite yielded an age of 550 ± 12 Ma (MSWD = 1.06). Whole-rock and mineral chemistry suggest that the studied rocks are calc-alkaline, having evolved by fractional crystallization of Ca- and Fe-Mg minerals under high oxygen fugacity. Using the amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer, we calculate temperatures and pressures of, respectively, 692-791 °C e 2.4-5.0 kbar for the intrusion of the PBJG, which is corroborated by previous metamorphic assemblages in the country rocks. The geological, geochemical and geochronological features of PBJG demonstrate their post-tectonic or post-collisional nature, with emplacement into an already uplifted and relatively cool crust at the end of brasiliano orogeny in this portion of the Tocantins Province.

Metamorphic investigation of mid-P aluminous gneisses from the central Grenville Province

This is a metamorphic study of mid-P anatectic aluminous gneisses from the Manicouagan and lac du Milieu areas of the central Grenville Province. The rocks are derived from hydrothermally altered felsic protoliths and were metamorphosed at granulite facies conditions during the Grenvillian orogeny. The samples come from three locations separated by several tens of kilometers and exhibit a wide range of textures and bulk compositions. However, they all have the same peak mineral assemblage: garnet + biotite + quartz + K-feldspar +/- plagioclase +/- sillimanite with retrograde cordierite in some, and show evidence of partial melting and melt loss. In terms of mineralogy and bulk composition, the samples were divided into two groups, sillimanite-rich and sillimanite-poor, with a high and low Alumina index in the AFM space, respectively. Phase equilibria modeling in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O– TiO₂–O (NCKFMASTHO) system using Thermocalc constrained the P–T field of the peak mineral assemblage at 800–900ºC and 6–11kbar, with melt solidification in the range of 800–865ºC and 6–8kbar. The presence of sillimanite inclusions in garnet, and of only scarce, retrograde cordierite, is consistent with moderate dP/dT gradient ‘hairpin’ P– T paths, which were similar between the three locations. This study also investigated the role of Fe3+ on phase stability in mid-P aluminous systems. Fe³⁺ is problematic because although it is incorporated in the NaCKFMASTHO system, it is rarely measured in modeled minerals and rocks and its value is generally assumed. Biotite may contain significant amounts of Fe³⁺, and these were analysed by Mössbauer spectroscopy in selected samples, where they were found to be low (0-4%). In addition, the effect of increasing the bulk Fe³⁺ in the mid-P portion of phase diagrams was modeled. This increase added new minor phases and changed the phase proportions, as well as shifted phase boundaries to a small degree, but P–T paths remained largely unaffected. Finally, the two methods commonly used in phase equilibria modeling to account for melt loss were compared. In some cases there were major differences in the topologies between the ‘melt reintegration’ and ‘adding water’ methods, but the former method is the most consistent with the rock data, and should be the method of choice.

Age determination on monazite from Forefinger Point granulites, East Antarctica (Table 2.6-1)

Electron microprobe (EMP) dating on monazite in granulite- facies rocks from Forefinger Point, East Antarctica, yielded dominant ages of 500 Ma on matrix monazites.They are associated with secondary cordierite, biotite and sapphirine, formed during nearly isothermal decompression after the high P-T assemblages involving garnet, orthopyroxene and sillimanite. Older ages around 750-1000 Ma are detected in monazite cores and in monazite inclusions in garnet porphyroblast. Combining the available age data and the reaction textures, it becomes evident that the Forefinger Point granulites have been overprinted by a granulite-facies decompressional event of Pan-African age. Moreover, EMP monazite dating imply that the Forefinger Point granulites have experienced at least two stages of metamorphic evolution.

Electron microprobe investigations of metamorphic reactions and mineral growth histories, Kwoiek area, British Columbia

The Kwoiek Area of British Columbia contains a pendant or screen of metamorphosed sedimentary and volcanic rocks almost entirely surrounded by a portion of the Coast Range Batholith, and intruded by several dozen stocks. The major metamorphic effects were produced by the quartz diorite batholithic rocks, with minor and later effects by the quartz diorite stocks. The sequence of important metamorphic reactions in the metasedimentary and metavolcanic rocks, ranging in grade from chlorite to sillimanite, is:

1. chlorite + carbonate + muscovite → epidote + biotite

2. chlorite + carbonate → actinolite + epidote

3. chlorite + muscovite → garnet + biotite

4. chlorite + epidote → garnet + hornblende

5. chlorite + muscovite → garnet + staurolite + biotite

6. chlorite + muscovite → aluminum silicate + biotite

7. muscovite + staurolite → garnet + aluminum silicate + biotite

8. staurolite → garnet + aluminum silicate

Continuous reactions, occurring between reactions 5 and 7, are:

A. chlorite + (high Ti) biotite + Al₂O₃ (from plagioclase?)→ garnet + staurolite + (low Ti) biotite + O₂

B. muscovite (phengitic) → garnet + staurolite +muscovite (less phengitic) + O₂ (?)

Detailed electron microprobe work on garnet, staurolite, biotite, and chlorite shows that:

(1) The garnet porphyroblasts are zoned according to a depletion model, called the Rayleigh depletion model, which assumes equilibrium between the edge of a growing garnet and the minerals which are unzoned, notably biotite, chlorite, and muscovite, but which assumes disequilibrium within the garnet.

(2) The staurolite porphyroblasts are also zoned, and from their zoning patterns reactions A, B, and 5 are documented. Progressive reduction of iron with increasing grade of metamorphism is also inferred from the staurolite zoning patterns.

(3) During a late period of falling temperature garnet continued to grow and the biotite and chlorite reequilibrated. The biotite, chlorite, and garnet edge compositions can vary from point to point in a given thin section, indicating that the volume of equilibrium at the final stage of metamorphism was only a few cubic microns.

(4) The horizon within the garnet that grew at maximum temperature can be identified. The Mg/Fe ratio of this horizon, if the garnet composition is a limiting composition in the Al₂O₃ - K₂O - FeO - MgO tetrahedron, increases systematically with increasing metamorphic grade. Biotite and chlorite compositions also show a general increase in Mg/Fe ratio with increasing metamorphic grade, but staurolite appears to show the reverse effect.

(5) The Mg/Fe ratio at the maximum temperature horizon of the garnet porphyroblasts is a function of its Mn content as evidenced from the study of five garnet-bearing rocks, collected from one outcrop area, with the same assemblage but with differing proportions of minerals.

An important implication of zoned minerals is that the effective composition of a system in a phase lies on the join between the homogeneous minerals (if there are two) and not within three-or- four-phase fields when a zoned mineral, such as garnet or staurolite, is present in the assemblage.

Study of the three aluminum silicates found in the Kwoiek Area showed that a constant pressure change in polymorphs from andalusite to kyanite to sillimanite took place with increasing temperature. This transition series is best explained by the metastable formation of andalusite.

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