Platinum-group minerals in chromitites from the ojen lherzolite massif (Serrania de Ronda,Betic Cordillera,Southern Spain)

Summary Chromitites (Cr ores) of the Ojen lherzolite massif (Serranía de Ronda, Betic Cordillera, Southern Spain) were found to contain platinum-group minerals (PGM) as discrete inclusions in the chromite and in the associated silicates. The PGM mineralogy consists of sulfides [laurite, erlichmanite, malanite, unnamed (Ni-Fe-Cu)₂ (Ir, Rh) S₃, unidentified Pd-S], sulfarsenides (irarsite, hollingworthite, ruarsite, and osarsite), arsenides [sperrylite, unidentified (Pd, Ni)-As], one unidentified Pd-Bi compound, and native platinum group elements (PGE) consisting of Ru and Pt-Fe alloys. Textural considerations suggest that the PGE chalcogenides with S and As were formed in the high-temperature magmatic stages, as part of the chromite precipitation event (primary PGM), in contrast with the native PGE, which originated during the low-temperature serpentinization of the ultramafic host of the chromitites (secondary PGM).The primary PGM inclusions in the Ojen chromite are unusual compared with PGM inclusions in chromitites from tectonitic upper-mantle of ophiolites and other alpine-type complexes in that i) they display a great variety of mineral species sulfides, sulfarsenides and arsenides, and ii) comprise specific phases of all six PGE. The singularity of the primary PGM mineralization probably reflects high activities of both S and As during chromite precipitation at Serrania de Ronda to be related with particular physico-chemical conditions during uplifting of sub-continental, astenospheric mantle.The nature, composition, and paragenetic association of secondary PGM at Ojen confirm the relatively-high mobility of the PGE at low temperature, and indicate that remobilization can be selective under appropriate redox conditions causing separation and redistribution of the PGE in the rocks as a result of the alteration process.

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Platingruppen-Minerale in chromititen aus dem ojen-lherzolithmassiv (Serranía de Ronda, Betische Kordillere, Süd-Spanien)

Zusammenfassung Platingruppen-Minerale in Chromititen aus dem Ojen-Lherzolithmassiv (Serranía de Ronda, Betische Kordillere, Süd-Spanien) In den Chromititen (Cr-Erzen) aus dem Ojen-Lherzolithmassiv (Serranía de Ronda, Betische Kordillere, Süd-Spanien) warden Platingruppen-Minerale (PGM) als einzelne Einschlüsse im Chromit and in den begleitenden Silikaten gefunden. Die Mineralogie der PGM setzt sich aus Sulfiden [Laurit, Erlichmanit, Malanit, einem unbenannten (Ni-Fe-Cu)₂ (Ir, Rh)S₃ und einem nicht identifizierten Pd-S], Sulfarseniden (Irarsit, Hollingworthit, Ruarsit und Osarsit), Arseniden [Sperrylit, einem nicht identifizierten (Pd, Ni)-As], einer nicht identifizierten Pd-Bi-Verbindung sowie gediegenen Platingruppen-Elementen (PGE) bestchend aus Ru and Pt-Fe-Legierungen, zusammen. Texturelle Untersuchungen haben ergeben, daß die PGE-Chalkogenide mit S und As im Zuge der Chromitfällung (primäre PGM) in den hochtemperierten, magmatischen Stadien gebildet warden, während die gediegenen PGE während der niedriggradigen Serpentini sierung des ultramafischen Nebengesteins der Chromitite (sekundäre PGM) gebildet warden.Die primären PGM-Einschlüsse in den Ojen-Chromiten sind im Vergleich zu PGM-Einschlüssen in Chromititen aus dem tektonisierten oberen Mantel in Ophiolithen und anderen alpinotypen Komplexen ungewöhnlich: i) Einerseits zeigen sie eine große Vielfalt an Mineralarten aus der Gruppe der Sulfide, Sulfarsenide und Arsenide. ii) Andererseits enthalten sie spezifische Phasen aller sechs PGE. Die Einzigartigkeit der primären PGM-Mineralisation könnte hohe Aktivitäten von S and As während der Chromit-Fällung in Serranía de Ronda widerspiegeln, die mit besonderen physiko-chemischen Bedingungen während der Hebung des subkontinentalen, asthenosphärischen Mantels zusammenhängen.Die Art, die Zusammensetzung and die paragenetische Vergesellschaftung von sekundären PGM in Ojen bestätigen die relativ hohe Mobilität der PGE bei niedriger Temperatur und zeigen, daß die Remobilisierung unter geeigneten Redox-Bedingungen selektiv wirken kann, wodurch eine Trennung und Neuverteilung der PGE in den Gesteinen als Ergebnis des Alterationsprozesses bewirkt wird.

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With 7 Figures     

The abundance of ammonium in the granites of central Spain,and the behaviour of the ammonium ion during anatexis and fractional crystallization

Summary The granites of the Sistema Central Espanol are richer in ammonium than those of most other regions, and have a mean NH₄ ⁺ content of 84 ppm (range = 1–243 ppm). Among the possible causes for the high level of ammonium, a high proportion of organic-rich pelitic protolith and reducing conditions during anatexis are considered to be the most significant. The behaviour of the ammonium ion during magmatic differentiation is discussed by reference to its distribution in the Pedrobernardo layered intrusion: ammonium is depleted in the final liquid fraction, but there is no relative fractionation of NH₄ ⁺ and K⁺. The depletion of the melt in NH₄ ⁺ during crystallization is attributed to its removal by biotite and to a lesser extent by K-feldspar. The behaviour of the ammonium ion during anatexis is discussed with reference to the Peña Negra migmatite complex. It is shown that large amounts of NH₄ ⁺ are present in these high grade metamorphic rocks, and that NH₄ ⁺ is preferentially partitioned into the restite fraction during partial melting. These relationships are attributed to the preferential incorporation of NH₄ ⁺ into potassic host minerals in the order: biotite > muscovite > K-feldspar.

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Ammonium in Zentralspanischen Graniten, und das Verhalten des Ammonium-Ions während Anatexis und fraktionierter Kristallisation

Zusammenfassung Die Granite des Sistema Central Espanol sind reicher an Ammonium als die der meisten anderen Regionen, und haben einen durchschnittlichen NH₄ ⁺ Gehalt von 84 ppm (von 1-243 ppm). Der hohe Ammoniumgehalt könme auf einen hohen Anteil peiitischer Ausgangsgesteine, die reich an organischen Material sind, and auf reduzierende Bedingungen während der Anatexis zurückgehen. Das Verhalten des Ammonium-Ions während magmatischer Differentiation wind in Hinblick seiner Verteilung in der geschichteten Intrusion von Pedrobernardo diskutiert: Ammonium ist in der finalen Schmelzfraktion angereichert, aber es gibt keine relative Fraktionierung von NH₄ ⁺ and K⁺. Die Verarmung der Schmelze an NH₄ ⁺ wahrend der Kristallisation geht darauf zurück, daß NH₄ ⁺ von Biotit and in einem geringen Ausmaß von K-Feldspat aufgenommen wird. Das Verhalten des Ammonium-Ions während der Anatexis wird am Peña Negra Migmatit-Komplex diskutiert. Es zeigt rich, daß große Mengen von NH₄ ⁺ in diesen hochgradig metamorphen Gesteinen vorkommen, and das NH₄ ⁺ während teilweiser Aufschmelzung vorzugsweise in der Restit-Fraktion angereichert wird. Diese Beziehungen gehen auf die vorzugsweise Aufnahme von NH₄ ⁺ in Kali-führenden Gastmineralen zurück, and zwar in folgender Ordnung: Biotit > Muskovit > K-Feldspat.

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Distribution and sources of pre-anthropogenic lead isotopes in deep ocean water from FeMn crusts

The lead isotope composition of ocean water is not well constrained due to contamination by anthropogenic lead. Here the global distribution of lead isotopes in deep ocean water is presented as derived from dated (ca. 100 ka) surface layers of hydrogenetic Fe-Mn crusts. The results indicate that the radiogenic lead in North Atlantic deep water is probably supplied from the continents by river particulates, and that lead in Pacific deep water is similar to that characteristic of island and continental volcanic arcs. Despite a short residence time in deep water (80–100 a), the isotopes of lead appear to be exceedingly well mixed in the Pacific basin. There is no evidence for the import of North Atlantic deep water-derived lead into the Pacific ocean, nor into the North Indian Ocean. This implies that the short residence time of lead in deep water prohibits advection over such long distances. Consequently, any climate-induced changes in deep-water flow are not expected to result in major changes in the seawater Pb-isotope record of the Pacific Ocean.     

Corrigendum: 1996. Residence of REE, Y, Th and U in Granites and Crustal Protoliths; Implications for the Chemistry of Crustal Melts

Owing to an error in a computer program, some of the LA—ICP—MSdata for yttrium presented in Tables 3, 4, 5, 6, 12 and 13 ofBea (1996) are incorrect. The following changes should be made:     

Suction-controlled experiments on Boom clay

The understanding of the thermo-hydro-mechanical behaviour of a clay barrier is needed for the prediction of its final in situ properties after the hydration and thermal transient in a radioactive waste repository.

As part of the CEC 1990–1994 R&D programme on radioactive waste management and storage, the CEA (Fr), CIEMAT (Sp), ENRESA (Sp), SCK · CEN (B), UPC (Sp) and UWCC (UK) have carried out a joint project on unsaturated clay behaviour (Volckaert et al., 1996). The aim of the study is to analyse and model the behaviour of a clay-based engineered barrier during its hydration phase under real repository conditions. The hydro-mechanical and thermo-hydraulic models developed in this project have been coupled to describe stress/strain behaviour, moisture migration and heat transfer. A thermo-hydraulic model has also been coupled to a geochemical code to describe the migration and formation of chemical species.

In this project, suction-controlled experiments have been performed on Boom clay (B), FoCa clay (Fr) and Almeria bentonite (Sp). The aim of these experiments is to test the validity of the interpretive model developed by Alonso and Gens (Alonso et al., 1990), and to build a database of unsaturated clay thermo-hydro-mechanical parameters. Such a database can then be used for validation exercises in which in situ experiments are simulated.

The Boom clay is a moderately swelling clay of Rupellian age. It is studied at the SCK · CEN in Belgium as a potential host rock for a radioactive waste repository. In this paper, suction-controlled experiments carried out on Boom clay by SCK · CEN are described. SCK · CEN has performed experiments to measure the relation between suction, water content and temperature and the relation between suction, stress and deformation. The applied suction-control techniques and experimental setups are detailed. The results of these experiments are discussed in the perspective of the model of Alonso and Gens. The influence of temperature on water uptake was rather small. The measured swelling-collapse behaviour can be explained by the Alonso and Gens model.     

Interparticle forces and displacements in granular materials

In a micromechanics framework, the main issue is the relationship between the microscale variables and the macroscale variables. These variables are used to describe either the statics or kinematics of the system. The relationships can be classified in two ways, namely, the “averaging” relationships and the “tracking” relationships. The averaging relationships express the macroscale variable as an averaging of the microscale variables; for example, the stress as a function of contact forces. The “tracking” relationships express the microscale variable as a function of the macroscale variables; for example, the contact force at a given orientation as a function of the stress. Based on fundamental premises, a unique averaging relationship exists for either the statics or the kinematics case. However, it is generally impossible to have a unique expression of the “tracking” relationship because they are generally derived with certain assumptions. In this paper, we will present expressions of the “tracking” based on three different approaches, namely, (1) energy conservation principle, (2) representation theory, and (3) indirect scheme. The assumptions used in each approach are discussed. The results are compared among the three approaches as well as that obtained from the Discrete Element Method (DEM).     

Mineral inclusions in diamonds from the Sputnik kimberlite pipe, Yakutia

The Sputnik kimberlite pipe is a small “satellite” of the larger Mir pipe in central Yakutia (Sakha), Russia. Study of 38 large diamonds (0.7-4.9 carats) showed that nine contain inclusions of the eclogitic paragenesis, while the remainder contain inclusions of the peridotitic paragenesis, or of uncertain paragenesis. The peridotitic inclusion suite comprises olivine, enstatite, Cr-diopside, chromite, Cr-pyrope garnet (both lherzolitic and harzburgitic), ilmenite, Ni-rich sulfide and a Ti-Cr-Fe-Mg-Sr-K phase of the lindsleyite-mathiasite (LIMA) series. The eclogitic inclusion suite comprises omphacite, garnet, Ni-poor sulfide, phlogopite and rutile. Peridotitic ilmenite inclusions have high Mg, Cr and Ni contents and high Nb/Zr ratios; they may be related to metasomatic ilmenites known from peridotite xenoliths in kimberlite. Eclogitic phlogopite is intergrown with omphacite, coexists with garnet, and has an unusually high TiO₂ content. Comparison with inclusions in diamonds from Mir shows general similarities, but differences in details of trace-element patterns. Large compositional variations among inclusions of one phase (olivine, garnet, chromite) within single diamonds indicate that the chemical environment of diamond crystallisation changed rapidly relative to diamond growth rates in many cases. P-T conditions of formation were calculated from multiphase inclusions and from trace element geothermobarometry of single inclusions. The geotherm at the time of diamond formation was near a 35 mW/m² conductive model; that is indistinguishable from the Paleozoic geotherm derived by studies of xenoliths and concentrate minerals from Mir. A range of Ni temperatures between garnet inclusions in single diamonds from both Mir and Sputnik suggests that many of the diamonds grew during thermal events affecting a relatively narrow depth range of the lithosphere, within the diamond stability field. The minor differences between inclusions in Mir and Sputnik may reflect lateral heterogeneity in the upper mantle.     

Nitrogen isotope indicators of seasonal source variability to groundwater

 A nitrogen isotope study of soil water and groundwater in southern Indiana, USA, in 1991–1992 demonstrated considerable variations in nitrate degradation processes compared to an earlier investigation in 1986–1987. Although N-fertilizers were applied in May 1991, the δ¹⁵N values in soil water decreased in February 1992, indicating its delayed release into the system after substantial rainfall. The δ¹⁵N values of groundwater decreased from +12.3‰ in November 1991 to +11.3‰ in February 1992, and to +7.5‰ in March 1992. The increased residence time of nitrate in the soil resulted in increased denitrification, ammonia volatilization and plant uptake, and reduced threat to the groundwater quality. The 1986–1987 study in the area reported that excessive rainfall during the summer rapidly transported the nitrate to deeper horizons and drastically reduced volatilization and microbial reduction of nitrate, thus increasing the immediate threat to the groundwater quality in the area. The present study demonstrated that nitrogen isotopic signatures can be used to determine the effects of local soil type, rainfall, and land-use practices on the fate of nitrate in the subsurface. Received: 18 February 1997 · Accepted: 17 June 1997     

Geochemistry and petrogenesis of Sikait leucogranite, Egypt: an example of S-type granite in a metapelitic sequence

 The Sikait leucogranite (SLG) is a body of porphyritic garnet granite intruded a metapelitic sequence and interlayered orthogneisses. Multiple deformation and low- to medium-grade metamorphism of the sequence was closely associated with pluton emplacement. Textural features of the SLG indicate that subsolidus plastic deformation was induced during the extensive thrusting. The granite is strongly peraluminous, alkali-rich and HFS (high field-strength) elements-depleted with low contents of REE, all facts that substantiate the geochemical characteristics of S-type granites. The geologic and geochemical features are consistent with a dehydration melting model of the hosted metapelites to generate the peraluminous SLG. However, geochemical modelling of trace elements and REEs suggest that the anatectic partial melt was subsequently affected by fractional crystallization of feldspars. This could explain much of the chemical attributes of SLG. Received: 20 September 1994 / Accepted: 2 August 1996