Experimental determination of the solubility of Au in silicate melts

Summary We report here new data on the solubility of Au in silicate melts of anorthite-diopside eutectic composition at a wide range of oxygen fugacities, from pure oxygen to 10^–8 atm, and at a temperature range of 1300 °C to 1480 °C. Because experiments were done with metal loops at temperatures above the Au-melting temperature, PdAu-metal-alloys had to be used. Pd-solubility data derived from the same set of experiments agree with earlier data obtained from experiments with pure Pd-metal (Borisov et al., 1994a). The results of the present experiments show that Pd-solubilities are by a factor of 2 to 6 higher than Au-solubilities. Both, Au and Pd solubilities decrease with decreasing oxygen fugacity. At oxygen fugacities below the iron-wiistite buffer (IW) Au solubility increases with decreasing fO₂ probably reflecting formation of Au-silicides at such reducing conditions. Compared to Pd, Au has higher activity coefficients in Fe-metal and lower solubility in silicate melts. This leads to similar metal-silicate partition coefficients for both elements. At a temperature of 1350 °C and an oxygen fugacity corresponding to IW-2 D^Au (met/sil) is about 2.5 · 10⁷ and D^Pd (met/sil) about 1.6 · 10⁷. Thus similar behavior is expected during metal separation in planetary bodies including core formation in the Earth. The metal/silicate partition coefficient of Ir is, however, by several orders of magnitudes higher (Borisov and Palme, 1995a). Equilibration with chondritic metal will therefore lead to grossly non-chondritic Pd/Ir or Au/Ir ratios in coexisting silicate phases. Chondritic ratios are thus indicative of the presence of unfractionated meteoritic components. Samples from the upper mantle of the Earth, for example, reflect the admixture of a late unfractionated (chondritic) veneer (e.g.,Kimura et al., 1974;Jagoutz et al., 1979).Solubilities of Pd and Au in silicate melts are much higher than the contents in terrestrial basalts implying that the abundances of these two elements are not buffered by residual PGE- and Au-containing alloys. The most likely process for fractionating PGEs in terrestrial magmas are mineral-melt (e.g., olivine/melt) equilibria.

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Experimentelle Bestimmung der Löslichkeit von Au in Silikatschmelzen

Zusammenfassung In der vorliegenden Arbeit wird über die Ergebnisse der Bestimmung der Löslichkeit von Au in Silikatschmelzen mit der Zusammensetzung des Anorthit-Diopsid Eutektikums berichtet. Die Versuche wurden mittels Metallschlaufe über einen weiten Sauerstoffpartialdruckbereich, von reinem Sauerstoff bis zu 10^–8 atm und in einem Temperaturbereich von 1300 °C bis 1480 °C, durchgeführt. Da diese Temperaturen jedoch den Au-Schmelzpunkt überschreiten, wurde mit AuPd-Legierungen gearbeitet. Die Ergebnisse der dadurch zusätzlich erhaltenen Pd-Versuche stimmen mit früher bestimmten, mit reinen Pd-Schlaufen durchgeführten Pd-Löslichkkeiten überein (Borisov et al., 1994a). Die auf reine Metalle zurückgerechneten Löslichkeiten von Pd sind um einen Faktor 2 bis 6 mal höher als die entsprechenden Au-Löslichkeiten. Die Löslichkeiten beider Metalle nehmen mit abnehmendem Sauerstoffpartialdruck ab. Unter noch stärker reduzierenden Bedingungen (Eisen-Wüstit Gleichgewicht) nimmt die Löslichkeit von Au jedoch zu. Dies könnte auf die Bildung von Au-Siliziden zurückzuführen sein.Im Vergleich zu Pd sind die Aktivitätskoeffizienten von Au in metallischem Eisen höher, die Löslichkeiten in Silikatschmelzen jedoch niedriger. Das führt zu ähnlichen Metall/Silikat Verteilungskoeffizienten von Au und Pd. Bei einer Temperatur von 1350 °C und einer Sauerstoffugazität von IW-2 ergeben sich für D^Au (met/sil) 2.5 · 10⁷ und für D^Pd (met/sil) 1.6* 10⁷. Der Metall/Silikat-Verteilungskoeffizient von Ir ist jedoch unter den gleichen Bedingungen um mehrere Größenordnungen höher (Borisov andPalme, 1995a). Ein chondritisches Pd/Ir- oder Au/Ir-Verhältnis kann also auf die Anwesenheit einer unfraktionierten chondritischen Komponente zurückgeführt werden. Dies gilt beispielsweise für Proben aus dem oberen Erdmantel. Hier handelt es sich vermutlich um Zumischung einer späten chondritischen Akkretionskomponente, die sich nicht mehr mit einer metallischen Phase (Kern) ins Gleichgewicht gesetzt hat (z.B.Kimura et al., 1974,Jagoutz et al., 1979).Die Löslichkeiten von Pd und Au in Silikatschmelzen sind wesentlich höher als ihre Gehalte in basaltischen und komatiitischen Laven. Dies bedeutet, daß Au und Pd in Schmelzen aus dem Erdmantel nicht durch residuale Au- und/oder Pd-haltige Metall phasen bestimmt sind. Gleichgewichte zwischen Schmelze und Mineralen (z.B. Olivin) sind die wahrscheinlichsten Fraktionierungsmechanismen für Platingruppenelemente in terrestrischen Magmen.

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With 5 Figures     

Policy concerns in Bulgarian food distribution

The Bulgarian food distribution system, like those of its Central and East European neighbours, lags behind the West in critical performance areas. Previous research quantified Central and East European food distribution deficiencies on the basis of a five factor model. This study investigates the attitudes of 250 Bulgarian consumers using these same five factors: food processing, quality, cost, availability and retailing. The findings show that the Bulgarian food distribution system does not satisfy consumer wants as well as do systems in other former communist countries in four of the five factors. At the same time, Bulgarian consumers are more satisfied than UK and US consumers in the system's ability to make some foods available. The study also shows that Bulgarian consumers who use privatised shops perceive the system more positively than those who use state and cooperative outlets. The implications of these and other findings are discussed in terms of critical policy concerns for government and industry stakeholders.     

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.     

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     

Dehydration melting of tonalites. Part I. Beginning of melting

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996     

The squeezing potential of rock around tunnels: Theory and prediction with examples taken from Japan

Summary Large deformations of surrounding media around tunnels are often encountered during excavations in rocks with squeezing characteristics. These deformations may sometimes continue for a long period of time. Predictions of deformations of tunnels in such grounds are urgently needed, not because of stability concerns, but also of their sevicability. In the present study, the squeezing phenomenon of rock around tunnels and its mechanism and associated factors are first clarified by carefully studying failures of tunnels, and a survey of tunnels in squeezing rocks in Japan is presented and its results are summarised. Then, a practical method is proposed to predic the squeezing potential and deformation of tunnels in squeezing rock and this method has beeen applied to actual tunnelling projects, where squeezing problems were encountered, to check its applicability and validity. Finally, an extension of this method to the time-dependent behaviour of squeezing rocks is given and an application of this method to an actual tunnel is presented.     

Dehydration melting of tonalites. Part II. Composition of melts and solids

 Dehydration melting of tonalitic compositions (phlogopite or biotite-plagioclase-quartz assemblages) is investigated within a temperature range of 700–1000°C and pressure range of 2–15 kbar. The solid reaction products in the case of the phlogopite-plagioclase(An₄₅)-quartz starting material are enstatite, clinopyroxene and potassium feldspar, with amphiboles occurring occasionally. At 12 kbar, zoisite is observed below 800°C, and garnet at 900°C. The reaction products of dehydration melting of the biotite (Ann₅₀)-plagioclase (An₄₅)-quartz assemblage are melt, orthopyroxene, clinopyroxene, amphibole and potassium feldspar. At pressures > 8 kbar and temperatures below 800°C, epidote is also formed. Almandine-rich garnet appears above 10 kbar at temperatures ≥ 750°C. The composition of melts is granitic to granodioritic, hence showing the importance of dehydration melting of tonalites for the formation of granitic melts and granulitic restites at pressure-temperature conditions within the continental crust. The melt compositions plot close to the cotectic line dividing the liquidus surfaces between quartz and potassium feldspar in the haplogranite system at 5 kbar and a _{H 2O} = 1. The composition of the melts changes with the composition of the starting material, temperature and pressure. With increasing temperature, the melt becomes enriched in Al₂O₃ and FeO+MgO. Potash in the melt is highest just when biotite disappears. The amount of CaO decreases up to 900°C at 5 kbar whereas at higher temperatures it increases as amphibole, clinopyroxene and more An-component dissolve in the melt. The Na₂O content of the melt increases slightly with increase in temperature. The composition of the melt at temperatures > 900°C approaches that of the starting assemblage. The melt fraction varies with composition and proportion of hydrous phases in the starting composition as well as temperature and pressure. With increasing modal biotite from 20 to 30 wt%, the melt proportion increases from 19.8 to 22.3 vol.% (850°C and 5 kbar). With increasing temperature from 800 to 950°C (at 5 kbar), the increase in melt fraction is from 11 to 25.8 vol.%. The effect of pressure on the melt fraction is observed to be relatively small and the melt proportion in the same assemblage decreases at 850°C from 19.8 vol.% at 5 kbar to 15.3 vol.% at 15 kbar. Selected experiments were reversed at 2 and 5 kbar to demonstrate that near equilibrium compositions were obtained in runs of longer duration. Received: 27 December 1995 / Accepted: 7 May 1996