Phase relations of osumilite and dehydration melting in pelitic rocks: a simple thermodynamic model for the KFMASH system

 Thermodynamic modelling of (1) osumilite solid solutions and (2) dehydration melting in pelitic compositions within the KFMASH system is quite successful in reproducing the invariant and univariant reactions determined in experimental studies. Even though rather preliminary, such melt thermodynamic models may be very useful in interpolating and extrapolating the limited information available from a small number of experimental runs. These methods allow the compositions of all phases to be monitored as a function of pressure, temperature and equilibrium phase assemblage for any desired bulk composition. Locating the higher variance phase fields (e.g. quadrivariant, quinivariant) is often difficult or impossible by inspection, but is made relatively easy using thermodynamic software such as thermocalc. In the KFMASH system the calculated partition of Fe and Mg between osumilite, garnet, cordierite, orthopyroxene and biotite are shown to be in good agreement with experimental and natural data and allow reliable calculation of mineral compositions coexisting with quartz-saturated and H₂O-undersaturated melts for a variety of bulk compositions. These phase diagram calculations allow quite tight limits to be placed on the pressure, temperature and water activity conditions which accompanied metamorphism of natural osumilite occurrences in Nain, Namaqualand, and Rogaland. At fixed bulk composition, the initial melting of pelites by dehydration of biotite can occur via univariant, divariant or trivariant equilibria depending upon pressure of metamorphism. Of particular interest is that, for low pressures or more magnesian bulk compositions, fluid-absent melting begins by generating liquid from the high-variance assemblage biotite+cordierite+K-feldspar+ quartz. This type of modelling allows investigation, at least qualitatively, of the fine scale details of melt production as a function of changes in pressure, temperature and bulk composition. Received: 29 November 1995 / Accepted: 22 April 1996     

Witwatersrand iron-formations and their significance for gold genesis and the composition limits of orthoamphibole

Summary In the West Rand Group of the 3.07–2.71 Ga old Witwatersrand Supergroup, South Africa, a series of banded iron-formations occur. They are of chemical origin and were deposited in an offshore shelf environment. The coarser-grained, in places pyrite-bearing, and partly auriferous metasedimentary rocks forming the bulk of the Witwatersrand Supergroup are regressive. The iron-formations, however, were deposited during transgression. The presence of allogenic pyrite in the fluviatile metaconglomerates and that of magnetite and, in places, haematite in the marine iron-formations suggests a lower pH and higher sulfur activity for the Archaean meteoric environment than for recent hydrothermal fluids on the ocean floor. Post-depositional alteration of the Witwatersrand rocks includes burial metamorphism at temperatures between 300 and 350 °C and pressures around 2.5 kbar, and multiple hydrothermal inflitration events at slightly lower temperatures, coeval with the brittle deformation of the basin fill during the deposition of the Transvaal Supergroup and the Bushveld Vredefort events.Additional thermal metamorphic overprint of the iron-formations around the Vredefort Dome caused the growth of orthoamphiboles. They show a wide range of compositions between ferro-anthophyllite and ferrous alumino-gedrite, suggesting that the crest of the solvus curve for Fe-rich orthoamphiboles is below 500 °C.Chlorite and amphibole compositions, and the presence of Fe-oxide-bearing horizons between pyrite-bearing ones indicate that the fluid composition during post-depositional alteration was largely controlled by the bulk rock composition of the infiltrated stratigraphic horizons and not by some external source.

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Zusammenfassung Die West Rand Group innerhalb der 3.07–2.71 Milliarden Jahre alten Witwatersrand Supergroup, Südafrika, führt eine Reihe von Magnetit- und Hämatit-haltigen Eisenformationen. Diese sind chemischen Ursprungs und wurden in einem flachmarinen Schelfmilieu abgelagert. Der überwiegende Teil der Witwatersrand Abfolge, bestehend aus klastischen, verschiedentlich Pyrit-führenden und teilweise goldhaltigen Metasedimentgesteinen, kann regressiven Phasen zugeschrieben werden. Die Eisenformationen wurden hingegen während transgressiven Phasen abgelagert. Aufgrund des Auftretens allogener Pyrite in den fluviatilen Konglomeratlagen und von Magnetit und Hämatit in den marinen Eisenformationen lassen sich für den meteorischen Bereich im Archaikum niedrigere pH-Werte und höhere Schwefelfugazität ableiten als für rezente submarine hydrothermale Fluide. Post-diagenetische Alterationsprozesse sind der Versenkungsmetamorphose mit Temperaturen zwischen 300 und 350 °C und Drucken um 2.5 kbar sowie etwas niedriger temperierten hydrothermalen Fluiden zuzuschreiben, die als Folge der inkompetenten Deformation der Beckenfüllung in diese während mehrer Stadien infiltrierten. Infiltration hydrothermaler Fluide während der Ablagerung der Transvaal Supergroup (2.55 Ga) und während des Bildung der Vredefort Struktur (2.0 Ga) sind durch Altersdaten belegt.Zusätzliche thermische Metamorphose der Fe-reichen Pelite und Eisenformationen im Bereich der Vredefort Struktur führte zur Bildung von Orthoamphibolen, deren Zusammensetzung von Anthophyllit bis zu Fe-reichem Alumino-Gedrit reicht. Dies läßt darauf schließen, daß die Solvuskurve für Fe-reiche Orthoamphibole unterhalb von 500 °C liegt.Die Zusammensetzung der Chlorite und Amphibole sowie das Auftreten von Fe-Oxid-führenden Horizonten in den generall Pyrit-reichen Metasedimentgesteinen gestatten die Annahme, daß die post-diagenetische Fluidzusammensetzung hauptsächlich durch die jeweilige Zusammensetzung der infiltrierten Gesteinshorizonte und nicht durch eine externe Quelle bestimmt wurde.

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With 8 Figures     

A low plain between arcadia and agronomy: Ippolito Nievo and the Friulan landscape

An analysis of the historical and cultural context of a large number of literary works illuminates the concept of landscape, a recurrent theme in contemporary humanistic geography. In this context, the works of Ippolito Nievo present an opportunity to look closer at the socio-economic circumstances of his time while also offering suggestive interpretative elements about the attitudes held concerning the wetlands of the lower Friulan plain.     

Spatial variations in the progress of land reform in Romania

Romania's socialist agricultural sector has been transformed by a series of measures taken after the revolution of 1989. A new farm structure is emerging out of the restitution provided for under the Land Law of 1991. There are striking spatial variations in different aspects of the privatisation process, especially the contrasting situations between the hill country (with heavy pressure on land) and the plains (where there is much better supply in relation to demand). Very small units of land ownership are being grouped into larger functional units for management by associations which are especially prominent in the main cropping zones. Meanwhile individual smallholdings are predominant in the hill and mountain zones. Despite a desire for owner-occupation, association is often advantageous through efficient deployment of machinery and some 40 percent of land allocated to individual peasants is being worked by some 20,000 associations. However, the situation has not yet stabilised and it is emphasised that small farms should be regarded not simply as agricultural units but as the cores of diversified enterprises characterised increasingly by pluriactivity     

The private sector and local economic development in South Africa

The objective in this paper is to analyse private sector involvement in LED in South Africa. Four key spheres of private sector involvement in LED are identified and discussed: (1) as participator and occasional initiator of local development processes, (2) as major partner in the development activities of public-private sector partnerships, (3) as lead role player in certain direct initiatives for reviving South Africa's inner cities, and (4) as promoter and facilitator of local small business development. It is argued that the concept of local dependence could be usefully applied to interpret private sector involvement in LED in South Africa.     

The thermodynamic properties of H2O in magnesium and iron cordierite

 The equilibrium water content of cordierite has been measured for 31 samples synthesized at pressures of 1000 and 2000 bars and temperatures from 600 to 750° C using the cold-seal hydrothermal technique. Ten data points are presented for pure magnesian cordierite, 11 data points for intermediate iron/magnesium ratios from 0.25 to 0.65 and 10 data points for pure iron cordierite. By representing the contribution of H₂O to the heat capacity of cordierite as steam at the same temperature and pressure, it is possible to calculate a standard enthalpy and entropy of reaction at 298.18° K and 1 bar for, (Mg,Fe)₂Al₄Si₅O₁₈+H₂O ⇄ (Fe,Mg)₂Al₄Si₅O₁₈.H₂O Combining the 31 new data points with 89 previously published experimental measurements gives: ΔH ^° _r =–37141±3520 J and ΔS ^° _r =–99.2±4 J/degree. This enthalpy of reaction is within experimental uncertainty of calorimetric data. The enthalpy and entropy of hydration derived separately for magnesian cordierite (–34400±3016 J, –96.5±3.4 J/degree) and iron cordierite (–39613±2475, –99.5±2.5 J/degree) cannot be distinguished within the present experimental uncertainty. The water content as a function of temperature, T(K), and water fugacity, f(bars), is given by n _H2O=1/[1+1/(K ⋅ f _H2O)] where the equilibrium constant for the hydration reaction as written above is, ln K=4466.4/T–11.906 with the standard state for H₂O as the gas at 1 bar and T, and for cordierite components, the hydrous and anhydrous endmembers at P and T. Received: 2 August 1994/Accepted: 7 February 1996     

Composition of hydrous melts in equilibrium with quartz eclogites

Summary Compositions of the hydrous melts in equilibrium with garnet, omphacitic clinopyroxene and quartz have been investigated experimentally at 28.5 and 35 kbar. They are represented by silica-rich liquids (> 70% SiO₂) with low MgO, FeO and CaO contents. The removal of ca 10–15% of the magma of this composition may be sufficient to convert quartz eclogite formed after subduction of altered MORB into a quartz-free bimineralic eclogite assemblage, which is a common type of xenoliths in kimberlites.At 28.5 kbar the solidus temperature is between 700 and 750° C in the system quartz eclogite—water, and the high pressure amphibole-out boundary lies at ca 25 kbar in accord with the previous studies.

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Die Zusammensetzung wasserhältiger Schmelzen im Gleichgewicht mit Quarz-Eklogiten

Zusammenfassung Um Prozesse zu simulieren, die bei der Subduktion von Ozeanbodenbasalten durch partielle Anatexis im Stabilitätsfeld von Eklogiten ablaufen, wurde die Zusammensetzung wasserhältiger Schmelzen in Gleichgewicht mit Granat, Omphacit und Quarz bei 28.5 und 35 Kbar experimentell untersucht. Diese Schmelzen sind reich an SiO₂ (> 70 Gew%) und arm an Mg0, Fe0 and CaO. Die Extraktion von ca. 10–15% derartiger Schmelzen würde genügen, um quarzführende Eklogite, die durch die Subduktion von alteriertem MORB Material entstanden sind, in quarzfreie bimineralische Eklogite umzuwandeln wie sie häufig als Xenolithe in Kimberliten beobachtet werden.Im System Quarz-Eklogit-Wasser liegt die Solidustemperatur bei 28.5 Kbar zwischen 700 und 750°C. Die obere Stabilitätsgrenze von Amphibol liegt in diesem Temperaturbereich bei ca. 25 Kbar.

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With 1 Figures     

Feasibility and cost of creating an iron-phosphate coating on pyrrhotite to prevent oxidation

 Acid mine drainage (AMD) occurs when sulfide minerals are exposed to an oxidizing environment. Most of the methods for preventing AMD are either short-term or high cost solutions. Coating with iron phosphate is a new technology for the abatement of AMD. It involves treating the sulfide with a coating solution composed of H₂O₂, KH₂PO₄, and sodium acetate as a buffer agent. The H₂O₂ oxidizes the sulfide surface and produces Fe³⁺ so that iron phosphate precipitates as a coating on the sulfide surface. Experiments performed under laboratory conditions prove that an iron phosphate coating can be established on pyrrhotite surfaces with optimal concentrations of the coating solution in the range of: 0.2M/0.01M H₂O₂, 0.2M KH₂PO₄, and 0.2M sodium acetate NaAc, depending on the experimental scale. Iron phosphate coating may be a long-term solution to the problem of AMD. The method would be easy to implement; the reagent cost, however, is not low enough, although it is lower than the conventional treatment with lime. Received: 30 March 1995 · Accepted: 6 September 1995     

Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.