Carte Métallogénique de la Bulgarie

Résumé On peut, en résumé, caractériser ainsi les principales provinces de la Bulgarie: — les Rhodopes constituent une zone typiquement polymétallique avec une prépondérance soulignée de Pb, Zn; le F, Cr, Ni, y existent en quantité subordonnée; en traces viennent encore: le Ba, Mn, Cd, Sb, W, Mo, Bi, As, Au, Ag, V; — la Sredna Gora est caractérisée comme une zone de cuivre typique, avec la présence de Fe, Mn, et en quantitée subordonnée de Pb, Zn, Mo, Ti, V, Au. — les Balkans portent les particularités d'une zone polymétallique (Pb, Zn, Cu) avec fer. On y remarque souvent des gîtes individualisés de cuivre, polymétallique avec fer, argent, ainsi que des gîtes complexes. Le Mn, Ba, Au, Ag, Co, Mo, As, Hg, V, W viennent en quantité subordonnée; — la zone des Kraistides, analogue à la précédente, se caractérise par des gisements polymétalliques pauvres et des gîtes à or et scheelite. Les éléments principaux sont: Au, Ba et secondaires: Pb, Zn, Cu, V et en partie du Fe et Hg; — la plateforme mésique, outre le gaz, se caractérise par le manganèse de la dépression de Varna.

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The metallogenic map of Bulgaria displays the following four major and distinct provinces: The Rhodopes as a typically polymetallic zone, mainly with Pb and Zn, but also with F, Cr and Ni, and minor or trace amounts of Ba, Mn, Cd, Sb, Mo, Bi, As, Au, Ag, V. The Sredna-gora is a distinct copper zone, with Fe and Mn, and minor amounts of Pb, Zn, Mo, Ti, V, Au. The Balkan is again a polymetallic zone of Pb, Zn and Cu with Fe; but Cu-Fe-Ag-deposits also occur. The other elements are present in minor quantities only. The Kraiste-Zone resembles the previous one and contains low grade polymetallic and scheelite deposits. The main elements are Au, Ba, and minor quantities of Pb, Zn, Cu, V and in part Fe and Hg. The zone of the Mésie platform contains only the manganese deposits of the Varna depression, in addition to natural gas.

     

Trace element concentrations of soils, plants and waters caused by a copper smelting plant and other industries, Northeast Turkey

The study area is situated in a large agricultural field which produces tobacco, maize, and other yearly cultivated vegetables in Tekkeköy, Samsun (NE-Turkey). In addition, a significant part of this area to the north along the Black Sea coast is occupied by several industrial plants such as a copper smelting plant (KB?), a fertilizer plant (Tügsa?) and industrial park facilities (IPF). In order to reveal their environmental impacts, heavy metal analyses were conducted on soil, plant leaves and water samples collected within an area of approximately 30 km² around these plants. Soil samples within an area of 10 km² around these facilities are found to be highly polluted with Cu, Zn, Pb, Fe and Mn. Pollution occurs at surface and sharply dies out at 20 cm downwards in soil profile. Since the region is polluted mostly with base metals, the copper smelting factory appears to be the main source of pollution as it processes the massive sulfidic ores of the Black Sea area. Plants show Cu, Pb, Zn and Fe pollution around KB? and Tügsa? and Cu and Pb around IPF. Pollutants observed in tobacco (Nicotiana tobacum) are Cu, Pb, Zn, Fe and S; in maize (Zea mays) Cu, Zn and Fe; and in cabbage (Brassica oleracea) Cu, Pb, Fe and S. The analyses of water samples collected from the study area reveal that Pb and, to a lesser degree, Cu and Fe pollution stem from KB?; Cu, Fe and Mn pollution from Tügsa?; Pb and minor amounts of Fe and Mn pollution from IPF. Factor analyses from analyzed metals and anionic complexes in water show three distinct groups: (a) an association of heavy metals with Na, K and Mg referring to pollution and acid leaching of soil, (b) an association of NH4, Fe, SO₄, Cl and Br indicating agricultural pollution and sea-water invasion in land near the shore line, and (c) HCO₃ behaving in a different manner in heavy metal precipitation.     

Iron,manganese and trace metal concentrations in seaweeds from the central west coast of the Gulf of California

Concentrations of Co, Cu, Fe, Mn, Ni, Pb and Zn in four macroalgae species (Ulva lactuca, Chondracanthus squarrulosus, Sargassum sinicola and Gracilariopsis lemaneiformis) were obtained for the first time from the central part of the west coast of the Gulf of California. Generally, no differences in metal concentrations were found among the different seaweed species, although spatial differences were apparent. Iron, Mn and Cu exhibited higher concentrations at the stations located in front of Angel de la Guarda Island, probably because of high vertical mixing processes present in the zone. The results were compared with dissolved metal concentrations reported for the Gulf of California (Cd, Mn and Fe) and the North Pacific Ocean. The resulting linear regression of the results vs. North Pacific Ocean concentrations indicated that the levels of Cu, Ni and Zn measured in this study were within its 95% confidence level. Furthermore, this comparison was capable of detecting dissolved Fe and Mn enrichments in Gulf of California waters relative to the North Pacific Ocean concentrations. Calculations of total masses of metals associated with algal biomass on the west coast of the Gulf of California indicated that the lowest masses were represented by Cu (108 ± 25 kg) and Ni (184 ± 52 kg), whereas Pb (1.1 ± 0.6 ton) and Fe (10.9 ± 8.5 ton) were the elements with the highest associated masses.     

The species of Silene compacta Fischer as indicator of zinc,iron and copper mineralization

The possibility of using the species Silene compacta Fischer (Caryophyllaceae) as a plant indicator for Zn, Fe and Cu is discussed in this paper. Rock and plant samples were collected from an area near Essimi, north-eastern Greece, which is known for its Cu–Pb–Zn mineralization and analyzed for their content in 14 elements (Fe, Mn, Ag, As, Cd, Co, Cu, Mo, Ni, Pb, Sb, Sn, Zn and V). The data illustrate positive linear correlation between the concentrations of Zn, Fe and Cu in plant ash and rock samples. In particular, these correlations are 0.99 for Zn, 0.97 for Fe and 0.97 for Cu and are significant at the 99.9% confidence level. Therefore, S. compacta could be used as a plant indicator for Zn, Fe and Cu mineralization.     

Sulfur Isotope Variations of Metallic Ore Deposits in the Gyeongsang Basin,South Korea

Many metallic ore deposits of the Late Cretaceous to Early Tertiary periods are distributed in the Gyeongsang Basin. Previous and newly analyzed sulfur isotope data of 309 sulfide samples from 56 ore deposits were reviewed to discuss the genetic characteristics in relation to granitoid rocks. The metallogenic provinces of the Gyeongsang Basin are divided into the Au–Ag(–Cu–Pb–Zn) province in the western basin where the sedimentary rocks of the Shindong and Hayang groups are distributed, Pb–Zn(–Au–Ag–Cu), Cu–Pb–Zn(–Au–Ag), and Fe–W(–Mo) province in the central basin where the volcanic rocks of the Yucheon Group are dominant, and Cu(–Mo–W–Fe) province in the southeastern basin where both sedimentary rocks of the Hayang Group and Tertiary volcanic rocks are present. Average sulfur isotope compositions of the ore deposits show high tendencies ranging from 2.2 to 11.7‰ (average 5.4‰) in the Pb–Zn(–Au–Ag–Cu) province, ?0.7 to 11.5‰ (average 4.6‰) in the Cu–Pb–Zn(–Au–Ag) province, and 3.7 to 11.4‰ (average 7.5‰) in the Fe–W(–Mo) province in relation to magnetite‐series granitoids, whereas they are low in the Au–Ag(–Cu–Pb–Zn) province in relation to ilmenite‐series granitoids, ranging from ?2.9 to 5.7‰ (average 1.7‰). In the Cu(–Mo–W–Fe) province δ³⁴S values are intermediate ranging from 0.3 to 7.7‰ (average 3.6‰) and locally high δ³⁴S values are likely attributable to sulfur derived from the Tertiary volcanic rocks during hydrothermal alteration through faults commonly developed in this region. Magma originated by the partial melting of the ³⁴S‐enriched oceanic plate intruded into the volcanic rocks and formed magnetite‐series granitoids in the central basin, which contributed to high δ³⁴S values of the metallic deposits. Conversely, ilmenite‐series granitoids were formed by assimilation of sedimentary rocks rich in organic sulfur that influenced the low δ³⁴S values of the deposits in the western and southeastern provinces.     

A GIS-based approach for detecting pollution sources and bioavailability of metals in coastal and marine sediments of Chabahar Bay,SE Iran

Chabahar Bay in SE of Iran is a shallow semi-enclosed environment affected by anthropogenic activities. In this paper, 19 sediment samples were collected and concentration of selected metals (Cu, Pb, Zn, Cd, Ni, Cr, Co, V and Fe) was determined using ICP-MS analytical method. Sediment samples from five stations were also selected for sequential extraction analysis and concentration of metals in each fraction was determined using ICP-OES. In order to investigate the environmental quality of Chabahar Bay, geographic information system (GIS) along with geochemical data, environmental indices and statistical analyses were used. Calculated contamination degree (C_d) revealed that most contaminated stations (Ch3, S1 and S3) are located SE of Chabahar Bay and contamination decreases in a NW direction. The S9 station, west of the bay, is also contaminated. High organic matter (OM) content in the sediments is most likely the result of fuel and sewage discharge from fishing vessels along with discharge of fishing leftovers. Significant correlation coefficient among OM, Fe, Cu, Pb, Zn and Cd seemingly reflects the importance of the role that OM and Fe oxy-hydroxides play in the metals mobility. The results of hierarchical cluster analysis (HCA), computed correlation coefficient and sequential extraction analysis suggest that Cu, Pb, Zn and Cd probably come from antifouling and sea vessel paints, while Ni, Cr, Co, V and Fe are most likely contributed by ophiolitic formations located north of the bay and/or deep sea sediments. Average individual contamination factors (ICFs) indicated that the highest health hazard from the bay is posed by Cu, Pb and Zn.     

Appareil ignimbritique et minéralisation cuprifère: Alous (Anti-Atlas,Maroc)

Résumé Le gisement d'Alous (4 à 6 Mt à 0,8% Cu) est un exemple apparemment fort rare, de dépôt de cuivre dans un appareil ignimbritique. Celui dans lequel il est installé appartient à une formation volcanique post-orogénique de la fin du Précambrien. Les sulfures de cuivre (chalcocite, bornite avec accessoirement chalcopyrite et pyrite) et les minéraux accompagnateurs (chlorites, séricite, albite, épidote, quartz) ont cristallisé dans des pyromérides au cours du refroidissement de l'ignimbrite. La minéralisation cuprifère est localisée le long de failles radiales et l'on observe une diminution centrifuge des rapports Cu/Fe des sulfures et Mg/Fe des chlorites. Un modèle de circulations hydrothermales associées au volcanisme ignimbritique est proposé: le cuivre aurait été lessivé à partir des laves basiques sous-jacentes puis redéposé sous forme de sulfures le long des failles radiales au cours du refroidissement des ignimbrites.

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The Alous deposit (from 4 to 6 Mt at 0.8% Cu) is apparently a rare example of copper deposit in ignimbrite volcanos. The volcano from which it comes belongs to a post-orogenic volcanic formation of late Proterozoic age (Anti-Atlas, Morocco). The copper sulphides (chalcocite, bornite with accessory chalcopyrite and pyrite) and associated minerals (chlorites, sericite, albite, epidote, quartz) crystallized during the cooling of the ignimbrite and were included in pyromeride textures. The mineralization is distributed along radial faults and displays, outwards from the volcano center, a decrease of sulphides Cu/Fe ratio and chlorites Mg/Fe ratio. A model of small-scale hydrothermal circulations linked to the volcanic activity is proposed: copper was leached from the underlaying basic lavas then redeposited along radial faults during the ignimbrite cooling.

     

Iron, manganese, and lead at Hawaii Ocean Time-series station ALOHA: Temporal variability and an intermediate water hydrothermal plume

Trace metal clean techniques were used to sample Hawaii Ocean Time-series (HOT) station ALOHA on seven occasions between November 1998 and October 2002. On three occasions, full water-column profile samples were obtained; on the other four occasions, surface and near-surface euphotic zone profiles were obtained. Together with three other published samplings, this site may have been monitored for “dissolved” (≤0.4 or ≤0.2 μm) Fe more frequently than any other open ocean site in the world.Low Fe concentrations (<0.1 nmol kg⁻¹) are seen in the lower euphotic zone, and Fe concentrations increase to a maximum in intermediate waters. In the deepwaters (>2500 m), the concentrations we observe (0.4-0.5 nmol kg⁻¹) are significantly lower than some other deep North Pacific stations but are similar to values that have been reported for a station 350 miles to the northeast. We attribute these low deepwater values to transport of low-Fe Antarctic Bottom Water into the basin and a balance between Fe regeneration and scavenging in the deep water. Near-surface waters have higher Fe levels than observed in the lower euphotic zone. Significant temporal variability is seen in near-surface Fe concentrations (ranging from 0.2-0.7 nmol kg⁻¹); we attribute these surface Fe fluctuations to variable dust deposition, biological uptake, and changes in the mixed layer depth. This variability could occur only if the surface layer Fe residence time is less than a few years, and based on that constraint, it appears that a higher percentage of the total Fe must be released from North Pacific aerosols compared to North Atlantic aerosols. Surprisingly, significant temporal variability and high particulate Fe concentrations are observed for intermediate waters (1000-1500 m). These features are seen in the depth interval where high δ³He from the nearby Loihi Seamount hydrothermal fields has been observed; the total Fe/³He ratio implies that the hydrothermal vents are the source of the high and variable Fe.The vertical profile of Mn at ALOHA qualitatively resembles other North Pacific Mn profiles with surface and intermediate water maxima, but there are some significant quantitative differences from other reported profiles. The ≤0.4 μm Mn concentration is highest near the surface, decreases sharply in the upper 500 m, then shows an intermediate water maximum at 800 m and then decreases in the deepest waters; these concentrations are higher than observed at a station 350 miles to the northeast that shows similar vertical variations. It appears that there is a significant Mn gradient (throughout the water column) from HOT towards the northeast.Compared to the first valid oceanic Pb data for samples collected in 1976, Pb at ALOHA in 1997-1999 shows decreases in surface waters and waters shallower than 200 m. Pb concentrations in central North Pacific surface waters have decreased by a factor of 2 during the past 25 yr (from ∼65 to ∼30 pmol kg⁻¹); surface water Pb concentrations in the central North Atlantic and central North Pacific are now comparable. We attribute the surface water Pb decrease to the elimination of leaded gasoline in Japan and to some extent by the U.S. and Canada. We attribute most of the remaining Pb in Pacific surface waters to Asian emissions, more likely due to high-temperature industrial activities such as coal burning rather than to leaded gasoline consumption. A 3-year mixed-layer time series from the nearby HALE-ALOHA mooring site (1997-1999) shows that there is an annual cycle in Pb with concentrations ∼20% higher in winter months; this rise may be created by downward mixing of the winter mixed layer into the steep gradient of higher Pb in the upper thermocline (Pb concentrations double between the surface and 200 m). From 200 m to the bottom, Pb concentrations decrease to levels of 5-9 pmol kg⁻¹ near the bottom; for most of the water column, thermocline and deepwater Pb concentrations do not appear to have changed significantly during the 23-yr interval.     

The HCl-soluble iron,manganese, and copper contents of recent Indian ocean sediments off the eastern coast of Somalia

The HCl-soluble Fe, Mn, and Cu contents of Recent Indian Ocean Sediments off the eastern Coast of Somalia increases progressively away from the coast with decreasing grain size and carbonate content. The average Mn and Cu contents of the Indian Ocean deep-sea clay (0.56% Mn, 0.025% Cu, recalculated on a carbonate-free base) are between those of the Atlantic (0.40% Mn, 0.013% Cu) and the Pacific Ocean (0.94% Mn, 0.040% Cu).

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Zusammenfassung In den rezenten Sedimenten des Indischen Ozeans vor der Ostküste Somalias nehmen die salzsäurelöslichen Eisen-, Mangan- und Kupfergehalte vom Küstenbereich zur Tiefsee hin bei abnehmendem Karbonatgehalt und geringer werdender Korngröße kontinuierlich zu. Die durchschnittlichen Mn- und Cu-Konzentrationen des Tiefseetons aus dem Indischen Ozean (bezogen auf karbonatfreies Material) liegen mit 0,56 bzw. 0,025% zwischen denjenigen des Atlantischen (0,40% Mn, 0,013% Cu) und des Pazifischen (0,94% Mn, 0,040% Cu) Ozeans.

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Advanced report to Meteor-Forschungsergebnisse, Indian Ocean Expedition 1964/65, to be published in 1967/68     

Vertical migration of residual magma in the upper zone of the Bushveld Complex

Summary Migration of residual liquid can potentially affect the textures and mineral compositions in layered intrusions, but is difficult to conclusively demonstrate. In the Upper Zone of the Bushveld Complex a metabasaltic xenolith forms a locally impermeable horizon, which acted as a barrier to vertically migrating residua. Increased Ab content in plagioclase, and K₂O and Zr in whole-rock analyses in the anorthosite directly below the xenolith, compared to the same horizon along strike of the xenolith, demonstrate trapping of residual liquid and/or fluid beneath the xenolith.Comparison of Cu/Ni and Cu/S ratios of the mineralised anorthosite in the normal sequence and below the xenolith suggests that these are primary magmatic sulphides which crystallised within the anorthosite and are not derived by sinking of dense interstitial sulphide liquid originally associated with the overlying magnetite layer or introduced hydrothermally.

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Vertikale Migration von Restmagma in der Upper Zone des Bushveld-Komplexes

Zusammenfassung Die Migration von Restschmelzen kann Texturen und Mineralzusammensetzungen in geschichteten Intrusionen beeinflussen, jedoch ist es schwierig, dies eindeutig nachzuweisen. In der Upper Zone des Bushveld-Komplexes bildet ein metabasaltischer Xenolith einen lokal undurchlässigen Horizont, der für vertikal migrierte Residuen als Barriere fungierte. Erhöhte Ab-Gehalte in Plagioklas, sowie erhöhte K₂O und Zr-Werte in Gesamtgesteins-Analysen in Anorthosit direkt unterhalb des Xenolithen-verglichen mit der Zusammensetzung des gleichen Horizontes in Streichen des Xenolithen-weisen auf Konzentration von Restschmelzen und/oder Fluiden im Liegenden des Xenolithen hin. Der Vergleich von Cu/Ni und Cu/S Verhältnissen der mineralisierten Anorthosite in der normalen Abfolge mit denen unterhalb des Xenolithen zeigt, daß es sich hier um primäre magmatische Sulfide handelt, die innerhalb des Anorthosits kristallisierten. Diese Sulfide lassen sich nicht auf das Absinken von dichter Sulfidschmelze, die ursprünglich mit den überlagernden Magnetit-Bändern in Zusammenhang standen, und auch nicht auf hydrothermale Zufuhr zurückführen.

     

Geochemical fractionation of heavy metals in Chilka Lake (east coast of India)—a tropical coastal lagoon

Chilka lake, the largest coastal lagoon of Asia is one of the most dynamic ecosystems along the Indian coast. Historically the lagoon has undergone a considerable reduction in surface area due, in part, to input from natural processes but mostly due to human activities. The purpose of this investigation is to document the heavy metals' affinity for specific geochemical phases in the recently deposited sediments in the lagoon. Thirty-three samples were collected and analyzed for different geochemical phases of Fe, Mn, Cu, Cr, Ni, Pb, and Zn utilizing a sequential extraction scheme. In the nonlithogenous fraction, the exchangeable fraction was not geochemically significant, having <2% of the total metal concentration for all the elements. However, the carbonate fraction contained the following percentages of the total concentration: <1% Fe, 13% Mn, 6% Cu, 4% Cr, 8% Ni, 13% Pb, and 12% Zn, suggesting the detrital origin of the sediments. Reducible and organic matter-bound fractions were the significant phases in the nonlithogenous fraction, containing 9% Fe, 16% Mn, 15% Cu, 16% Cr, 16% Ni, 14% Pb, and 14% Zn in the former and 4% Fe, 3% Mn, 17% Cu, 3% Cr, 14% Ni, 15% Pb, and 14% Zn in the latter. The phenomenon has been attributed to the scavenging affinity of Fe-Mn oxides and affinity for sorption into organic matter of the lagoon sediments. The lithogenous, residual fraction generally considered as a guide for natural background values was determined to contain 87% Fe, 67% Mn, 61% Cu, 77% Cr, 61.3% Ni, 56% Pb, and 60% Zn of the total concentrations.     

The Relationship Between Mineralogical Characteristics and Isotopic Composition of Sphalerite,as Exemplified by the Huxu Deposit,China

The relationship between mineralogical characteristics and isotopic composition of sulfides has not received its proper share of attention from geologists, although many references are available concerning the application of sulfur isotopes to geological problems. Located in the vicinity of the contact region between the Yangtze Platform and the South China Caledonian Folding Zone, the Huxu deposit is hosted in a structural zone in quartz-diorite-porphyrite emplaced in Jurassic volcanic rocks. Sphalerite and galena are the principal ore minerals in the deposit. (1) Sphalerite is highly variable in color and this variation can be related to its chemical composition and sulfur isotopic characters. Dark colored sphalerites are poor in Zn and Ni, rich in Pb, Cu, Fe, Ag and Au and have high δ³⁴S values, while the opposite is true for light-colored ones. (2) δ³⁴S of sphalerite is negatively correlated with the contents of Zn and Ni and positively correlated with the contents of Pb, Cu, Ag and Au, with the absolute values of the correlation coefficients being greater than 0.7. The above two characters suggest that the sulfur isotopic composition of sphalerite is controlled not only by the physicochemical conditions under which the mineral was formed, but also by mineralogical characteristics of the host mineral. (3) Apparent correlations exist among the constituent elements in the sphalerite. For example, Zn is negatively correlated with Cu, Pb, Fe, Ag and Au and positively correlated with Ni. (4) Sphalerites of the same color in the same hand specimen always show similar characters with respect to trace element and sulfur isotopes. (5) Two distinct trends of evolution can be recognized between Zn and Cu, Zn and Pb, Zn and Ag and between these elements on one hand and δ³⁴S on the other, reflecting that the ore-forming solutions may have resulted from mixing of fluids of different origins. (6) Pb is uniformly distributed in sphalerite and shows positive correlations with Cu, Fe, Ag and δ³⁴S, suggesting isomorphic substitution in the sphalerite lattice. This project was financially supported by the Open Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences.     

Geochemistry of the M'Passa Pb-Zn deposit (Niari syncline,People's Republic of the Congo). Arguments in favor of a hydrothermal origin

The Pb-Zn deposits of the M'Passa mine are located on faults running in a Combian (i.e., N50°E) direction. The interpretation preferred by most authors over the last decade is that synsedimentary ore concentrations have been redistributed in the vicinity of fault zones. This paper presents the results of a detailed study of the behavior of 11 metallic elements (V, Mn, Fe, Co, Cu, Zn, Mo, Ag, Cd, Sb, Pb) systematically measured along a well-exposed section (94 samples, in 28 of which As was also measured). Principal component analysis of the data shows a regular decrease in the total metal content with increasing distance from the fault zones; it also brings to light groupings of metallic elements into a group of mobile elements (Pb, Zn, Cd) and a group of less mobile elements (Ag, Cu, Mo, Fe, Co). The latter are concentrated in and near the fault zone. This distribution corroborates a normal thermal zoning of elements issued from the faults rather than a lateral leaching of a preexisting ore concentration down the fault zone. A gradient in Fe content in sphalerite observed over both ore trends could also indicate regularly decreasing thermal conditions during ore formation. In addition, exploratory measurements of sulfur isotopes clearly indicate an ore concentration process different from an euxinic process. Other synsedimentary metal concentrations related to organic matter evolution seem difficult to reconcile with the total residual organic carbon content, and characteristic ratios regarding organic carbon do not show at the present time any relation with organic matter evolution. Rather than assuming that all organic indicators were erased during the geological evolution of the M'Passa deposit, a model is preferred in which local hydrothermal deposition issued from the fault and diffused through specific dolomitic strata. Paleokarstic features may be regarded as passive ore reservoirs or could be the result of alteration associated with hydrothermal fluids.

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Résumé Les concentrations Pb-Zn exploitées à M'Passa sont localisées sur des failles de direction combienne (N50°E). L'interprétation préférée par la plupart des auteurs de la dernière décennie suppose une préconcentration synsédimentaire, redistribuée dans des zones faillées. Les résultats de l'étude détaillée du comportement de 11 éléments métalliques (V, Mn, Fe, Co, Cu, Zn, Mo, Ag, Cd, Sb, Pb), dosés systématiquement le long de coupes continues (94 échantillons, dont 28 d'entre eux dosés aussi en As) ne permettent pas de confirmer cette hypothèse. L'analyse en composantes principales des teneurs met en évidence une décroissance régulière de la teneur en métaux en s'éloignant des zones faillées. Elle permet aussi de mettre en évidence des groupes de métaux dont une famille d'éléments plus mobiles (Pb, Zn, Cd) et une autre famille d'éléments moins mobiles (Ag, Cu, Mo, Fe, Co). Ces derniers sont concentrés préférentiellement à l'intérieur ou à proximité des zones faillées. Cette distribution s'accorderait davantage avec un zonage thermique normal enraciné dans les failles plutôt qu'avec une redistribution per-descensum de concentrations préexistantes. La décroissance régulière de la teneur en Fe de la blende, fonction de la distance à la faille et indépendante du type de minerai, pourrait aussi avoir été accompagnée d'un gradient thermique au cours du dépot. Quelques mesures exploratoires de constitution isotopique du soufre permettent aussi d'écarter une origine euxinique des sulfures. D'autres possibilités de concentration associée à l'évolution de matières organiques paraisent aussi difficiles à concilier avec la teneur résiduelle en carbone organique. L'absence de relation entre rapports organiques caractéristiques et nature du minerai ne permet pas de conclure à une relation avec l'évolution de la matière organique. Donc, plutôt que considérer que tout marqueur organique aurait été effacé au cours de l'évolution géologique postérieure au dépot, on préfère dans l'état actuel des connaissances un modèle apparenté à une précipitation hydrothermale initiée dans les zones faillées et prolongée latéralement dans des nìveaux dolomitiques spécifiques. Les traits paléokarstiques de ces niveaux seraient alors à envisager, soit comme des réservoirs passifs, soit comme le résutat de l'altération d'épontes par des fluides hydrothermaux.

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G. Buffet present address: INRIA, Avenue Emile Hugues, Sophia Antipolis, France-06565 Valbonne Cedex (reprints)     

40Ar/39Ar age constraints on deformation and mineralization, Rosebery Zn-Pb-Cu and Mount Lyell Cu deposits, Tasmania, Australia

The ⁴⁰Ar/³⁹Ar dating of alteration muscovite from the Rosebery Zn-Pb-Cu and Mount Lyell Cu deposits, Tasmania, Australia, has determined a succession of deformation events which occurred from 400-378 Ma, and comprises the Devonian Tabberabberan Orogeny. The dates from Rosebery range from 400-390 Ma, are a minimum age for mineralization, indicate the time of deformation, and provide a maximum age limit for granitoid emplacement in the vicinity of the deposit. The ages from the Mount Lyell field range from 400-378 Ma, are a minimum for mineralization, and date cleavage development. The North Lyell Cu mineralization, which was probably broadly coeval with deformation, may have formed at 400 Ma. All pre-Devonian alteration micas in the Rosebery and Mount Lyell areas have been recrystallized or reset. The Tabberabberan deformation in western Tasmania was broadly contemporaneous with widespread crustal shortening in southeastern Australia, as established from the dating of alteration minerals associated with deformation-related precious and base metal deposits.     

多壁碳纳米管固相萃取快速检测水样中铅镉铜铁

传统的固相萃取填料应用于环境样品的重金属处理过程中,存在pH不稳定和不同极性萃取物共同萃取较为困难等方面的不足,因此寻找新型固相萃取填料显得尤为重要。本文采用多壁碳纳米管填充固相萃取柱,萃取水中金属元素铅、镉、铜和铁,采用石墨炉原子吸收光谱法测定铅和镉,电感耦合等离子体发射光谱法测定铜和铁。实验考察了多壁碳纳米管的性质、溶液pH值、洗脱溶液、样品流速以及基体效应对测定结果的影响。结果显示:溶液pH=9,1 mol/L硝酸为洗脱溶液,样品流速为2 mL/min时,外径8 nm未修饰的多壁碳纳米管有较好的萃取效率,对溶液中铅、镉、铜和铁的最大吸附容量分别为44.91、42.31、54.68和49.07 mg/g,四种元素的吸附容量均衡;钾、钠、钙、镁离子以及苯和甲苯等基质对四种金属元素的萃取影响不大。方法回收率为95.3%~99.5%,精密度(RSD,n=7)为1.2%~3.2%。本方法采用外径8 nm的多壁碳纳米管固相萃取,与传统萃取方法相比,富集效果好、回收率较高,而且操作简便、准确度高;与前人采用外径20~30 nm的多壁碳纳米管的性能相比,镉和铜的吸附容量更高,还可实现对铁的吸附,且铅、镉、铜和铁四种元素的吸附容量均衡,更适合用于检测水样中的金属元素。     

Trace metal nanoparticles in pyrite

Hydrothermal pyrite contains significant amounts of minor and trace elements including As, Pb, Sb, Bi, Cu, Co, Ni, Zn, Au, Ag, Se and Te, which can be incorporated into nanoparticles (NPs). NP-bearing pyrite is most common in hydrothermal ore deposits that contain a wide range of trace elements, especially deposits that formed at low temperatures. In this study, we have characterized the chemical composition and structure of these NPs and their host pyrite with high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), analytical electron microscopy (AEM), and electron microprobe analysis (EMPA). Pyrite containing the NPs comes from two types of common low-temperature deposits, Carlin-type (Lone Tree, Screamer, Deep Star (Nevada, USA)), and epithermal (Pueblo Viejo (Dominican Republic) and Porgera (Papua New-Guinea)).EMPA analyses of the pyrite show maximum concentrations of As (11.2), Ni (3.04), Cu (2.99), Sb (2.24), Pb (0.99), Co (0.58), Se (0.2), Au (0.19), Hg (0.19), Ag (0.16), Zn (0.04), and Te (0.04) (in wt.%). Three types of pyrite have been investigated: “pure” or “barren” pyrite, Cu-rich pyrite and As-rich pyrite. Arsenic in pyrite from Carlin-type deposits and the Porgera epithermal deposit is negatively correlated with S, whereas some (colloform) pyrite from Pueblo Viejo shows a negative correlation between As + Cu and Fe. HRTEM observations and SAED patterns confirm that almost all NPs are crystalline and that their size varies from 5 to 100 nm (except for NPs of galena, which have diameters of up to 500 nm). NPs can be divided into three groups on the basis of their chemical composition: (i) native metals: Au, Ag, Ag–Au (electrum); (ii) sulfides and sulfosalts: PbS (galena), HgS (cinnabar), Pb–Sb–S, Ag–Pb–S, Pb–Ag–Sb–S, Pb–Sb–Bi–Ag–Te–S, Pb–Te–Sb–Au–Ag–Bi–S, Cu–Fe–S NPs, and Au–Ag–As–Ni–S; and (iii) Fe-bearing NPs: Fe–As–Ag–Ni–S, Fe–As–Sb–Pb–Ni–Au–S, all of which are in a matrix of distorted and polycrystalline pyrite. TEM-EDX spectra collected from the NPs and pyrite matrix document preferential partitioning of trace metals including Pb, Bi, Sb, Au, Ag, Ni, Te, and As into the NPs. The NPs formed due to exsolution from the pyrite matrix, most commonly for NPs less than 10 nm in size, and direct precipitation from the hydrothermal fluid and deposition into the growing pyrite, most commonly for those > 20 nm in size. NPs containing numerous heavy metals are likely to be found in pyrite and/or other sulfides in various hydrothermal, diagenetic and groundwater systems dominated by reducing conditions.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.     

Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Contribution á l'étude du comportement géochimique de quelques éléments métalliques dans la sédimentogenèse

Résumé Les traces de Cu, Pb, Cd, Ni et Zn ont été dosées par polarographie sur une centaine d'échantillons du Trias et du Jurassique. La confrontation des résultats obtenus et des faits géologiques tend à démontrer que la répartition des oligoéléments a été essentiellement déterminée par les paramètres qui définissent l'environnement et le milieu de dépôt. En ce qui concerne l'environnement de dépôt, le comportement différent lors de l'altération du Ni d'une part, et du Zn et du Cd d'autre part, s'interprète très bien par la théorie du champ des ligands. En ce qui concerne le milieu de dépôt, l'étude plus particulière de l'Hettangien qui localement recèle des concentrations de blende et de galène, démontre que l'on passe sans discontinuité brutale du domaine des traces à celui des concentrations et ceci, en relation avec l'accentuation du caractère réducteur du milieu. De plus, les formes minéralogiques d'entraînement des cinq éléments dosés, ainsi que le pH et Ia teneur en soufre (sous ses différentes formes: S⁼, HS^– et H₂S) du milieu de dépôt et du milieu de piégeage sont déterminées à l'aide des calculs de corrélation, des règles de coprécipitation et d'adsorption et des diagrammes log S—pH.

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Polarographic quantitative analysis of Cu, Pb, Cd, Ni and Zn in one hundred Triassic and Jurassic samples show that the repartition of these trace elements has been mainly fixed by the parameters of the depositional environment. The differences between the behaviour of Ni, Zn and Cd during alteration is explained mainly by the ligand field theory. The study of the Hettangian sediments especially those containing local ZnS and PbS deposits show that there is no discontinuity in the repartition of the studied elements from the non-mineralized sediments to the mineralized area, but shows a regular variation with increasing reducing character of the depositional medium. The mineralogical forms of coprecipitation or adsorption of these elements, the pH and the concentration of the total sulfur (under the form S⁼, HS^– and H₂S) of the normal depositional medium and of the reducing zone are determined by using correlation calculations, coprecipitation and adsorption rules and log S—pH diagrammes.