Petrology and alteration geochemistry of the epithermal Balya Pb-Zn-Ag deposit,NW Turkey

The 1.5 km-large hydrothermal system of Balya is characterized by three alteration styles which from the outer halo towards the center are: (i) propylitic alteration with the hydrothermal mineral assemblage of calcite-daphnite-albite-epidote-quartz-pyrite; (ii) argillic/phyllic alteration with the hydrothermal mineral assemblage of sericite/muscovite-kaolinite-rutile-quartz ± pyrite; (iii) advanced argillic alteration with the hydrothermal mineral assemblage of alunite-jarosite-kaolinite-quartz-sericite ± pyrite. Hornblende andesite is the protolith of the hydrothermal alteration system. Enrichment in Si, Sb and Rb, and depletion in Na, Ca, Mg, Fe, Mn, P, Ba, Sr, and Zn distinguishes the argillic/phyllic and advanced alteration types from propylitic alteration and the unaltered hornblende andesite protolith. REE distribution patterns indicate an essentially immobile behaviour of REEs during the alteration cycle. K-Ar age data for unaltered and hydrothermally altered rocks define a synchronous age of 25.3 ± 1.2 Ma for both igneous and hydrothermal activity.     

Calculations of activity-composition relations in multi-site solid solutions: the example of AB2O4 spinels

A model to calculate activities in multisite solutions like spinels, from a general expression of the Gibbs free energy is developped. The free energy is written as that of a solution with ideal mixing of cations on each sublattice corrected by any suitable higher order terms. It is shown that activities of i^th end-member can be simply written: $${\text{act (}}i{\text{) = (}}\gamma _i {\text{/}}\gamma _i^{\text{0}} {\text{)}}\mathop \prod \limits_j (N_j /N_j^0 )^{P(j,{\text{ }}i)} .$$ N _j are site occupancy fractions; the γ _i are equal to one for the ideal multisite model and depend only on the higher order corrections to this model; ⁰ indicate values for the i ^th end member. The exponents in the matrix P are integers and constants. The activities cannot be expressed explicitly as function of the macroscopic composition. The site occupancy fractions which minimize the Gibbs free energy must be calculated first solving a set of non linear equations which define the internal equilibrium conditions. The (Fe²⁺, Mg) (Al, Cr, Fe³⁺) spinel are used to illustrate these calculations. For multicomponent AB₂O₄ spinels activity expressions derived for the reference ideal multisite mixing model are: $${\text{act (AB}}_{\text{2}} {\text{O}}_{\text{4}} {\text{) = }}\frac{{({\text{A}})[{\text{B}}]^2 }}{{({\text{A}})_0 [{\text{B}}]_0^2 }}$$ (A): fraction of tetrahedral sites occupied by A²⁺; [B]: fraction of octahedral sites occupied by B³⁺. Because the site occupancy fractions at equilibrium are not independent (but related by the internal equilibrium relations) many equivalent expressions of the activities can be obtained. Finally approximations proposed in the literature to obtain simple explicit activity-concentration relationships are discussed.     

An EPR study of Mn2+ and Fe3+ in dolomites

Electron paramagnetic resonance (EPR) measurements on dolomites from 9 different localities revealed contents of Mn²⁺ on two axial sites in all of them. The center with largerzero-field splitting (ZFS) was always present in much higher concentrations, except for a sample from Oberdorf it amounted to 95 percent or more of the total. This dolomite was the only one with a considerable content of Fe³⁺ on one axial site, almost certainly substituting for Mg²⁺. With X-ray irradiation the concentration of Fe³⁺ increased by about 30 percent showing that at least some of the divalent iron also substitutes for Mg. The ZFSs for Fe³⁺ and Mn²⁺ with larger ZFS increase with decreasing temperature in the same manner. The previous assignment of this Mn²⁺ to Mg sites is thus confirmed. An almost regular increase of the trigonal distortions at the divalent ions in different carbonates with increasing ionic radius is indicated by their crystal structure data. The very small ZFS for Mn²⁺ on Ca sites in dolomite must thus result from a strong local relaxation in the direction of a more regular octahedral arrangement. It is difficult to explain the different distribution ratios of Mn²⁺ on Ca and Mg sites with differences in growth and/or annealing temperatures alone. Thus different supply of Mg²⁺ and Ca²⁺ in the growth solutions may also contribute.     

Tin granites,geochemical heritage,magmatic differentiation

Metallogenic provinces are not self-evident geochemical provinces. A scheme to quantify the processes of »geochemical heritage« and »magmatic differentiation« in the evolution of tin granites is presented. Geochemical heritage can be limited to a maximum contribution in the 5–10 ppm Sn range. The crucial process in the formation of tin granites is magmatic differentiation. A variable bulk Sn distribution coefficient controls the tin ore potential of granites.

---

Zusammenfassung Metallogenetische Provinzen stehen nicht zwangsläufig mit einer spekulativen regionalen geochemischen Spezialisierung im Zusammenhang. Am Beispiel der Zinngranite wird ein Schema zur Quantifizierung der beiden Komponenten »geochemische Vererbung« und »magmatische Differentiation« vorgestellt. Geochemische Vererbung kann dabei auf den Bereich von maximal 5–10 ppm Sn eingegrenzt werden. Entscheidender Prozess für die Bildung von Zinngraniten ist die magmatische Differentiation, wobei ein variabler Bulk-Zinn-Verteilungskoeffizient das mögliche Zinn-Potential bestimmt.

---

Résumé Les provinces métallogéniques ne correspondent pas nécessairement à des domaines à permanence géochimique. Prenant l'exemple des granites à étain, l'auteur présente un schéma qui quantifie les deux composants que sont »l'héritage géochimique« et la »différenciation magmatique«. L'héritage géochimique peut Être limité à une contribution maximale de 5 à 10 ppm Sn. Le processus décisif dans la formation des granites à étain est la différenciation magmatique, au cours de laquelle le coefficient de répartition de Sn est variable et détermine le potentiel-métal du granite.

---

. , , . 5–10 . .

     

New hole centers in natural quartz

In natural citrines five new hole centers were detected and analyzed by electron paramagnetic resonance. An additional one was observed in rose-colored quartz crystals with radiation defects as the cause of coloration. Characteristic hyperfine patterns due to an adjacent aluminum impurity were resolved in the spectra of three of these centers. Their relations to other hole centers of well-known structure in quartz and fused silica are discussed and possible models for their structures are proposed.     

Efficiency of heavy liquid separation to concentrate magnetic particles

Low-temperature rock magnetic measurements have distinct diagnostic value. However, in most bulk marine sediments the concentration of ferrimagnetic and antiferromagnetic minerals is extremely low, so even sensitive instrumentation often responds to the paramagnetic contribution of the silicate matrix in the residual field of the magnetometer. Analysis of magnetic extracts is usually performed to solve the problems raised by low magnetic concentrations. Additionally magnetic extracts can be used for several other analyses, for example electron microscopy or X-ray diffraction. The magnetic extraction technique is generally sufficient for sediments dominated by magnetite. In this study however, we show that high-coercivity components are rather underrepresented in magnetic extracts of sediments with a more complex magnetic mineralogy. We test heavy liquid separation, using hydrophilic sodium polytungstenate solution Na₆[H₂W₁₂O₄₀], to demonstrate the efficiencies of both concentration techniques. Low-temperature cycling of zero-field-cooled, field-cooled and saturation isothermal remanent magnetization acquired at room temperature was performed on dry bulk sediments, magnetic extracts, and heavy liquid separates of clay-rich pelagic sediments originating from the Equatorial Atlantic. The results of the thermomagnetic measurements clarify that magnetic extraction favours components with high spontaneous magnetization, such as magnetite and titanomagnetite. The heavy liquid separation is unbiased with respect to high- and low-coercive minerals, thus it represents the entire magnetic assemblage.     

Gold overprint of PGE alloy: an example from the Fadeevka Au-PGE placer, Russian Far East

Summary We document a rare case of micron-sized gold inclusions in Ir–Os alloy and overgrowth rims on Pt–Fe alloy from an alluvial Au-PGE placer derived from an Uralian/Alaskan type intrusion in Primorye, Russia. The gold inclusions occasionally form complex aggregates with cooperite [PtS] or tolovkite [IrSbS], and replace magmatic inclusions of Ir-rich Pt–Fe alloy which exsolved from the Ir–Os–Pt matrix. Gold has a relatively constant composition (>90 wt.% Au, a few wt.% Ag, and up to 8 wt.% Pt). The gold rims form superfine (3–5 μm) discontinuous films on the Pt–Fe alloy crystals often followed by cooperite overgrowth. Both gold textures suggest an electrochemical control of gold precipitation via selective Pt–Fe leaching during low-temperature overprint and/or weathering of PGE alloy.     

Slowness-backazimuth weighted migration: A new array approach to a high-resolution image

We have developed a new array method combining conventional migration with a slowness-backazimuth deviation weighting scheme. All seismic traces are shifted based on the theoretical traveltime of the scattered wave from specific gridpoints in a 3-D volume. Observed slowness and backazimuth are calculated for each raypath and compared with theoretical values in order to estimate slowness and backazimuth deviations. Subsequently, stacked energy calculated by a conventional migration method is weighted by the slowness and backazimuth deviations to suppress any arrival energy whose slowness and backazimuth are inconsistent with the expected theoretical values. This new method was applied to two P- wave data sets which comprise (1) underside reflections at the 410 and 660 km mantle discontinuities and (2) D" reflections as well as their corresponding synthetic data sets. The results show that the weighting scheme dramatically increases the resolution of the migrated images and enables us to obtain well-constrained, focused images, making upper-mantle discontinuities and D" reflections more distinct by reducing their surrounding energy.