The age and thermal history of Cerro Rico de Potosi, Bolivia

 Cerro Rico de Potosi, Bolivia, is the world’s largest silver deposit and has been mined since the sixteenth century for silver, and for tin and zinc during the twentieth century, together with by-product copper and lead. The deposit consists primarily of veins that cut an altered igneous body that we interpret to be a dacitic volcanic dome and its underlying tuff ring and explosion breccia. The deposit is compositionally and thermally zoned, having a core of cassiterite, wolframite, bismuthinite, and arsenopyrite surrounded by a peripheral, lower-temperature mineral assemblage consisting principally of sphalerite, galena, lead sulfosalt, and silver minerals. The low-temperature assemblage also was superimposed on the high-temperature assemblage in response to cooling of the main hydrothermal system. Both the dacite dome and the ore fluids were derived from a larger magmatic/hydrothermal source at depth. The dome was repeatedly fractured by recurrent movement on the fault system that guided its initial emplacement. The dome was extruded at 13.8±0.2 Ma (2σ), based on U-Th-Pb dating of zircon. Mineralization and alteration occurred within about 0.3 my of dome emplacement, as indicated by a ⁴⁰Ar/³⁹Ar date of 13.76±0.10 Ma (1σ) for sericite from the pervasive quartz-sericite-pyrite alteration associated with the main-stage, high-temperature, mineralization. The last thermal event able to reset zircon fission tracks occurred no later than 12.5±1.1 Ma (1σ), as indicated by fission-tract dating. Minor sericite, and magmatic-steam alunite veins, were episodically formed around 11 Ma and between 8.3 and 5.7 Ma; the younger episodes occurring at the time of extensional fracturing at Cerro Rico and widespread volcanism in the adjacent Los Frailes volcanic field. None of these younger events appear to be significant thermal/mineralizing events; the exceptionally flat thermal release pattern of ³⁹Ar from sericite and the results of the fission-tract dating of zircon show that none of the younger events was hot enough, and lasted long enough, to cause significant loss of Ar or annealing of zircon fission tracks. U-Th-Pb dating of zircon cores indicates a Precambrian progenitor for some zircons, and REE analyses of dated samples of hydrothermally altered dacite show the presence of a prominent positive Eu anomaly, which constrains interpretations of the origin and evolution of the magmatic/hydrothermal system. Received: 14 October 1995/Accepted: 29 January 1996     

Field assessment of acid mine drainage contamination in surface and ground water

Both sulfate and conductivity are useful indicators of acid mine drainage (AMD) contamination. Unlike pH, they are both extremely sensitive to AMD even where large dilutions have occurred. The advantage of using sulfate to trace AMD is that unlike other ions it is not removed to any great extent by sorption or precipitation processes, being unaffected by fluctuations in pH. These two parameters are also closely associated as would be expected, as conductivity is especially sensitive to sulfate ions. Therefore, as sulfate analysis is difficult in the field, conductivity can be used to predict sulfate concentration in both AMD and contaminated surface waters using regression analysis. Most accurate predictions are achieved by using equations given for specific conductivity ranges or AMD sources. There is also potential to use conductivity to predict approximate concentrations of key metals when the pH of the water is within their respective solubility ranges.     

Pore-water response on seasonal environmental changes in intertidal sediments of the Weser Estuary,Germany

In order to determine time-dependent changes in estuarine pore-water chemistry and flux variations across the sediment-water interface, sediment cores of an intertidal mud flat in the Weser Estuary were taken monthly over a one-year period. Sediment temperature, pH, Eh, Cl^–, O₂, NO ₃ ^– , and SO ₄ ^2– pore-water concentrations were measured and showed variations that relate to the changes of surface temperature and estuarine water composition. Fick's first law was applied to quantify diffusive fluxes from concentration gradients in the diffusive boundary layer and in the pore water. Total nitrate fluxes were calculated from flux chamber experiments. Diffusive oxygen fluxes increased from 5 mmol m^–2 d^–1 in winter to 18 mmol m^–2 d^–1 in early summer, while nitrate fluxes into the sediment increased from 3 mmol m^–2 d^–1 in winter to 60 mmol m^–2 d^–1 in early summer. Oxygen and nitrate fluxes into the sediment correlated linearly to sediment temperature. Sulfate fluxes increased from 0.5 mmol m^–2 d^–1 in winter to 10 mmol m^–2 d^–1 in August and September. Converted into carbon fluxes, the sum of these oxidants ranged from 10 mmol m^–2 d^–1 in winter to 80 mmol m^–2 d^–1 in summer. An estimation of the upper limit of the annual nitrate flux into the sediment showed that about 10% of the 250,000 t of nitrate discharged annually by the river may be decomposed within the inner Weser Estuary.     

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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With 5 Figures     

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).