Influence of sedimentary environments on sulfur isotope ratios in clastic rocks: a review

Strata-bound sulfide deposits associated with clastic, marine sedimentary rocks, and not associated with volcanic rocks, display distributions of S³⁴ values gradational between two extreme types: 1. a flat distribution ranging from S³⁴ of seawater sulfate to values about 25 lower; and 2. a narrow distribution around value S³⁴ (sulfide)=S³⁴ (seawater sulfate) –50, and skewed to heavier values. S³⁴ (seawater sulfate) is estimated from contemporaneous evaporites. There is a systematic relation between the type of S³⁴ distribution and the type of depositional environment. Type 1 occurs in shallow marine or brackish-water environments; type 2 occurs characteristically in deep, euxinic basins. These distributions can be accounted for by a model involving bacterial reduction of seawater sulfate in systems which range from fully-closed batches of sulfate (type 1) to fully open systems in which fresh sulfate is introduced as reduction proceeds (type 2). The difference in the characteristic distributions requires that the magnitude of the sulfate-sulfide kinetic isotope effect on reduction be different in the two cases. This difference has already been suggested by the conflict between S³⁴ data for modern marine sediments and laboratory experiments. The difference in isotope effects can be accounted for by Rees' (1973) model of steady-state sulfate reduction: low nutrient supply and undisturbed, stationary bacterial populations in the open system settings tend to generate larger fractionations.

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Zusammenfassung Schichtgebundene Sulfid-Lagerstätten in Begleitung von klastischen, marinen Sedimentgesteinen ohne Beteiligung vulkanischer Gesteine zeigen kontinuierliche Verteilungen der S³⁴-Werte zwischen zwei Extremtypen: 1. Eine flache Verteilung im Bereich von S³⁴-Werten des Seewasser-Sulfats bis zu Werten, die etwa 25 niedriger liegen. 2. Eine eng begrenzte Verteilung um den S³⁴ (Sulfid)-Wert=S³⁴ (Seewasser-Sulfat) –50 und asymmetrischer Verteilungskurve mit stärkerer Besetzung bei den schwereren Werten. Das S³⁴ (Seewasser-Sulfat) wird von gleichaltrigen Evaporiten abgeleitet. Es besteht eine systematische Beziehung zwischen der Art der S³⁴-Verteilung und dem Milieu des Ablagerungsraumes. Typ 1 tritt im marinen Flachwasser oder in brackischer Umgebung auf. Typ 2 ist charakteristisch für tiefe euxinische Becken. Diese Verteilungen können erklärt werden mit Hilfe eines Modells mit bakterieller Reduktion von Meerwasser-Sulfat in Systemen, die von völlig abgeschlossenen Sulfat-Mengen (Typ 1) bis zu völlig offenen Systemen reichen, in die bei fortschreitender Reduktion frisches Sulfat zugeführt wird (Typ 2). Der Unterschied in den charakteristischen Verteilungen setzt voraus, daß die Stärke der kinetischen Sulfat-Sulfid-Isotopen-Wirkung auf die Reduktion in beiden Fällen verschieden ist. Dieser Unterschied wurde bereits wegen der Widersprüche zwischen den verschiedenen S³⁴-Werten heutiger mariner Sedimente und Laborexperimente vermutet. Der Unterschied in der Isotopen-Wirkung kann durch das Modell von Rees (1973) für kontinuierlich ablaufende Sulfat-Reduktion erklärt werden. Geringes Nahrungsangebot und ungestörte, gleichbleibende Bakterien-Populationen in offenen Systemen neigen zur Erzeugung stärkerer Fraktionierungen.

     

Formation of Mud-Volcanic Fluids in Taman (Russia) and Kakhetia (Georgia): Evidence from Boron Isotopes

Temperatures of the formation of mud-volcanic waters are determined based on concentrations of some temperature-dependent components (Na–Li, Mg–Li). Estimates obtained for the Taman and Kakhetia regions are similar and range from 45 to 170°, which correspond to depths of 1–4.5 km. The calculated temperatures correlate with the chemical (Li, Rb, Cs, Sr, Ba, B, I, and HCO₃) composition of water and ¹³ (₂) and ¹³ (CH₄) values in spontaneous gases. The isotope values indicate that mechanisms of the formation of ¹³-rich gases, i.e., gases with high ¹³ values (up to +16.0 in ₂ and –23.4 in CH₄) in mud-volcanic systems of Taman and Kakhetia are governed by fluid-generation temperatures rather than the supply of abyssal gases. The ¹¹ value was determined for the first time in mud-volcanic products of the Caucasus region. This value ranges from +22.5 to +39.4 in the volcanic water of Georgia, from –1.2 to +7.4 in the clayey pulp of Georgia, and from –7.6 to +13.2 in the clayey pulp of Taman. It is shown that the ¹¹ value in clay correlates with the fluid-generation temperature and ¹¹ correlates with ¹³ in carbon-bearing gases. These correlations probably testify to the formation of different phases of mud-volcanic emanations in a single geochemical system and suggest the crucial role of temperature in the development of isotope-geochemical features.     

Sulfur isotope ratios of Icelandic rocks

Sulfur isotope ratios have been determined in 27 selected volcanic rocks from Iceland together with their whole rock chemistry. The ³⁴S of analyzed basalts ranges from –2.0 to +0.4 with an average value of –0.8 Tholeiitic and alkaline rocks exhibit little difference in ³⁴S values but the intermediate and acid rocks analyzed have higher ³⁴S values up to +4.2 It is suggested that the overall variation in sulfur isotope composition of the basalts is caused by degassing. The small range of the ³⁴S values and its similarity to other oceanic and continental basalts, suggest that the depleted mantle is homogeneous in its sulfur isotope composition. The ³⁴S of the depleted mantle is estimated to be within the range for undegassed oceanic basalts, –0.5 to +1.0     

Sulfur isotopes and origin of some sulfide deposits,New England,Australia

The S-isotopic compositions of sulfide deposits from Steinmann, granitoid and felsic volcanic associations have been examined. Ores of Steinmann association have ³⁴S values close to zero per mil (³⁴S=+0.3±3.1) it appears they are of mantle origin. Isotopically, ores of granitoid association regularly show a variable enrichment in ³²S relative to meteoritic (³⁴S=–2.7±3.3). The composition is in accord with an upper mantle/lower crustal source. Two stratiform accumulations of felsic volcanic association show a narrow spread of ³⁴S values (+0.2 to 2.4); a mantle origin for the sulfur in these deposits is favored. In contrast, vein, stockwork and cement ores are moderately enriched in ³²S relative to meteoritic (³⁴S=–4.0±6.4). These ores are polygenetic; sulfur and metals appear to have been leached from local country rocks where volcanogenic and biogenic sulfur predominate.     

Sulphur and sulphate-oxygen isotopes and the origin of the silvermines deposits,Ireland

New sulphur and sulphate-oxygen isotope measurements for the main discordant and stratiform lead-zinc-barite orebodies at Silvermines Co. Tipperary, allow reappraisal of previously offered differing interpretations (Graham, 1970; Greig et al., 1971) of the bearing of sulphur isotopes on the genesis of this important Irish deposit. The following aspects of the data are confirmed: barite ³⁴ S-values range from 17–21, similar to lower Carboniferous seawater sulphate: stratiform sulphide lens pyrites have ³⁴ S-values ranging from –13 to –36; vein sulphide ³⁴ S-values range from –8 to 4; sulphide ³⁴ S-values increase upwards and outwards respectively in the related discordant and stratiform G orebodies; galena-sphalerite isotope palaeotemperatures are not too consistent, ranging from 40 to 430°C (using the calibration of Czamanske and Rye (1974). New facts are as follows: barite ¹⁸O-values range from –13 to –17, stratiform barites ranging from 13 to 14.5; sulphides separated from a single stratiform ore lens hand specimen usually have ³⁴ S_sl > ³⁴ S_ga > ³⁴ S_py; the outward decrease in ³⁴ S-values in the stratiform G orebody is confined to the first few hundred feet only; pyrite ³⁴ S-values progressively increase downwards through one stratiform sulphide orebody; yet variations of 13 occur within a single colloform pyrite structure from another stratiform orebody. It is concluded that there were at least two sources of sulphur, seawater sulphate and deep-seated sulphur. The former was the dominant source of all sulphate and, via biogenic reduction, of the sulphur in the bulk of the stratiform sulphide. The latter was the source of the sulphur in the vein sulphides. There was minimal isotopic interaction between the cool seawater sulphate and the warm unwelling ore fluid sulphur species, even though the latter precipitated under near isotopic equilibrium conditions when the temperature dropped and/or the pH and Eh increased. The lack of isotopic equilibrium between pyrite and ore sulphides in the stratiform ore lenses may result from the latter having precipitated slightly later than the former because of solubility relationships. Overall the present isotopic evidence supports considerable geological evidence favoring a syngenetic origin for the stratiform Silvermines orebodies.     

Schwefel- und Sauerstoff-Isotopenanalysen von Sulfaten des Kupferschiefers

Zusammenfassung Zur Bestimmung der O¹⁸-Werte von Sulfaten wird BaSO₄ mit Kohlenstoff reduziert und das gewonnene CO₂ massenspektrometrisch gemessen. Das sehr einfache Reduktionsverfahren erlaubt eine Meßgenauigkeit von 0,4 relativ zur SMOW-Skala.Eine kombinierte Schwefel- und Sauerstoffisotopenanalyse von Gips bzw. Anhydrit sollte Einzelheiten über Entstehung und Herkunft dieser Sulfate erkennen lassen. Am Beispiel eines Kupferschieferprofiles wird gezeigt, daß durch eine derartige Analyse primäre Restsulfate von sekundär zu Sulfaten aufoxidierten Sulfiden unterschieden werden können. Die sekundären Sulfate sind durch relativ leichten Sauerstoff (O¹⁸=+4)gekennzeichnet und an S³⁴ verarmt (S³⁴–23), was auf den Zusammenhang mit den durch bakterielle Reduktion gebildeten Kupferschiefersulfiden schließen läßt (Einzelheiten vgl. Marowsky, 1969). Die primären Restsulfate sind dagegen an O¹⁸ und S³⁴ angereichert. Die von Lloyd (1968) gefundene Korrelation zwischen der Anreicherung von schwerem Schwefel und schwerem Sauerstoff in dem verbleibenden Sulfat bei bakterieller Sulfatreduktion konnte bestätigt werden.

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Sulfur and oxygen isotope studies of sulfates from the Permian Kupferschiefer

The oxygen isotopic composition of sulfates has been determined in CO₂ by mass spectrometry after reduction of BaSO₄ with carbon. The experimental procedure with a precision of 0.4 in the scale relative to SMOW is described in some detail. It is a problem to distinguish between primary and secondary gypsum or anhydrite in argillaceous sediments. A combined analysis of sulfur and oxygen of the sulfates mentioned is applied for getting evidence on the origin of these sulfates. Samples of a Permian Kupferschiefer profile show that primary residual sulfates from closed systems can be distinguished from secondary sulfates formed from oxidized sulfides. These secondary sulfates are characterized by relatively light oxygen (O¹⁸+4 relative to SMOW) and sulfur (S³⁴-23), which is due to their origin from sulfides of bacterially reduced sulfates. The primary residual sulfates are enriched in O¹⁸ and S³⁴. The correlation of heavy sulfur with heavy oxygen during bacterial reduction of sulfates (Lloyd, 1968) could be confirmed.

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Die massenspektrometrischen Messungen wurden von der Deutschen Forschungsgemeinschaft durch die Einrichtung des Zentrallabors für Geochemie der Isotope an der Universität Göttingen ermöglicht. Herrn Prof. Dr. K. H. Wedepohl und den Mitarbeitern des Zentrallabors danke ich für wertvolle Ratschläge und Diskussionsbereitschaft.     

Schwefelisotopenuntersuchungen an einigen Sulfid- und Sulfatmineralen der Blei-Zink-Erzlagerstätte Bleiberg/Kreuth,Kärnten

Zusmmenfassung Die Ergebnisse der Schwefelisotopenanalysen von sechs Sulfid- und vier Sulfatmineralproben von Bleiberg/Kreuth (Österreich) variieren von –6,9 bis –25,9 ³⁴S in den Sulfiden und von +14,8 bis +18,9 ³⁴S in den Sulfaten. Die große Variationsbreite der Schwefelisotopen und die Bevorzugung des leichten Schwefels deutet vermutlich auf bakterielle Prozesse der Sulfidfällung. Die Sulfatschwefel fallen in den Bereich der Schwefelisotopenzusammensetzung des mesozoischen (postskytischen) Meerwassers.

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Determination of the sulfur isotopic composition in some sulfide and sulfate minerals of the lead zinc deposit, Bleiberg/Kreuth, Carinthia

Summary Results of sulfur isotope analyses on 6 sulfides and 4 sulfates from Bleiberg/Kreuth (Austria) range from –6.9 to –25.9 ³⁴S (in sulfides) and from +14.8 to +18.9 ³⁴S (in sulfates). A large range of sulfide sulfur isotope fractionation with appreciable light sulfur probably indicates a bacterial sulfur source in sulfide precipiation. The sulfate sulfur plots in the range of Mesozoic (post-Skytian) seawater sulfur isotopic composition.

     

Isotope studies on the Rosebery,Mount Farrell and Mount Lyell ores,Tasmania

Preliminary studies have been made on the distributions of oxygen and sulphur isotopes in the Rosebery, Mount Farrell, and Mount Lyell ores. These ores lie in Cambrian geosynclinal volcanic rocks in West Tasmania. At each locality the sulphur of the sulphide minerals has a distinctive degree of enrichment in ³⁴S in relation to sulphur in meteorites and a narrow range of ³⁴S values. The dominant ore at Mount Lyell (mainly pyrite-chalcopyrite) has an average ³⁴S value of +7.0, the main lode at Rosebery (pyrite-sphalerite-galenachalcopyrite) averages +10.9, and the Mount Farrell ore (galena-sphalerite) averages +14.1. The degree of enrichment does not appear to be related to local, near-surface geological factors. Other ores of geosynclinal volcanic type with similar mineralogy also show narrow ranges in ³⁴S and varying enrichments in ³⁴S. Barite from a concordant sulphide-barite-carbonate lode at Rosebery has an average ³⁴S of +38.1 and an average ¹⁸O of +10.7. Barite from veins at Mount Lyell has an average ³⁴S of +25.3 and an average ¹⁸O of +10.6.

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Die Verteilung von Sauerstoff- und Schwefel-Isotopen in den Erzkörpern von Rosebery, Mount Farrell und Mount Lyell wurde untersucht. Die Erzkörper sind in kambrische, geosynklinale vulkanische Gesteine Westtasmaniens eingebettet. An jeder dieser Lagerstätten zeigt der Schwefel der Sulfiderze einen charakteristischen Anreicherungsgrad an ³⁴S im Verhältnis zum Meteoritenschwefel und einen eng begrenzten Bereich der ³⁴S-Werte. Die Erze des Mount Lyell-Lagers (hauptsächlich Pyrit-Chalkopyrit) zeigen überwiegend einen ³⁴S-Durchschnittswert von +7.0, das Hauptlager von Rosebery (Pyrit-Sphalerit-Galenit-Chalkopyrit) +10.9, und des Mount Farrell-Erz (Galenit-Sphalerit) +14.1. Der Anreicherungsgrad scheint nicht mit den lokalen geologischen Faktoren verbunden zu sein. Auch andere Erzkörper geosynklinaler vulkanischer Art von ähnlicher mineralogischer Struktur zeigen eng begrenzte ³⁴S-Werte und ³⁴S-Anreicherungsvariationen. Der Baryt des konkordant aufgebauten Sulfid-Baryt-Carbonat-Lagers bei Rosebery hat einen ³⁴S-Durchschnitt von +38.1 und einen ¹⁸O-Durchschnitt von +10.7. Der Baryt aus den Erzgängen von Mount Lyell ist durch einen ³⁴S-Durchschnitt von +25.3 und einen ¹⁸O-Durchschnitt von +10.6 charakterisiert.

     

A sulfur isotope study of volcanogenic massive sulfide deposits of the Eastern Black Sea province,Turkey

Kuroko-type massive sulfide deposits of the Eastern Black Sea province of Turkey are related to the Upper Cretaceous felsic lavas and pyroclastic rocks, and associated with clay and carbonate alteration zones in the footwall and hangingwall lithologies. A complete upward-vertical section of a typical orebody consists of a stringer-disseminated sulfide zone composed mainly of pyrite and chalcopyrite; a massive pyrite zone; a massive yellow ore consisting mainly of chalcopyrite and pyrite; a black ore made up mainly of galena and sphalerite with minor amounts of chalcopyrite, bornite, pyrite and various sulfosalts; and a barite zone. Most of the deposits in the province are associated with gypsum in the footwall or hangingwall. The paragenetic sequence in the massive ore is pyrite, sphalerite, chalcopyrite, bornite, galena and various sulfosalts, with some overlap between the mineral phases. Massive, stringer and disseminated sulfides from eight kuroko-type VMS deposits of the Eastern Black Sea province have a ³⁴S range of 0–7 per mil, consistent with the ³⁴S range of felsic igneous rocks. Sulfides in the massive ore at Madenköy (4.3–6.1 per mil) differ isotopically from sulfides in the stringer zone (6.3–7.2 per mil) suggesting a slightly increased input of H₂S derived from marine sulfate with time. Barite and coarse-grained gypsum have a ³⁴S range of 17.7–21.5 per mil, a few per mil higher than the ³⁴S value of contemporaneous seawater sulfate. The deposits may, therefore, have formed in restricted basins in which bacterial reduction of sulfate was taking place. Fine-grained, disseminated gypsum at Kutlular and Tunca has ³⁴S values (2.6–6.1 per mil) overlapping those of ore sulfides, indicating sulfide oxidation during waning stages of hydrothermal activity.     

Geology and geochemistry of the Changba SEDEX Pb-Zn deposit,Qinling orogenic belt,China

The Changba Pb-Zn SEDEX deposit occurs in the Middle Devonian sequence of the Anjiaca Formation of the Western Qinling Hercynian Orogen in the Gansu Province, China. The Changba-II orebody is hosted in biotite quartz schist and is the largest of 143 stratiform orebodies that are hosted either in biotite quartz schist or marble. The Changba-II comprises two types of mineralization: a bedded facies and an underlying breccia lens. The bedded section exhibits three sulfide sub-facies zoned from bottom to top: 1) banded sphalerite intercalated with quartz albitite; 2) interbedded massive pyrite and sphalerite ore; and 3) banded sphalerite ore intercalated with banded baritite. Major metallic minerals are sphalerite, pyrite, galena, with minor arsenopyrite, pyrrhotite, boulangerite, and rare chalcopyrite. The bedded sulfides are underlain by a lens of brecciated and albitized biotite-quartz schists cemented by sulfides and tourmaline.Massive and bedded sulfide ³⁴S values range from 8.1 to 29.3, whereas barite ³⁴S values range from 20.8 to 31.5. Disseminated pyrite in footwall schists has ³⁴S values ranging from 8.1 to 10.6, and increase to values ranging from 11.1 to 14.7 in the hangingwall. The lower ³⁴S values for massive and bedded sulfides are interpreted to be derived from progressive bacterial sulfate reduction (BSR) of Devonian seawater in a sulfate-restricted sub-basin. The higher ³⁴S values for massive and bedded sulfides could be a product of quantitative BSR but this is incompatible with barite being more abundant above the bedded sulfides. Instead, it is more likely that thermochemical sulfate reduction of seawater sulfate or of evaporite was the source of heavy hydrothermal sulfur. Heavy hydrothermal sulfur was injected into a sulfate-restricted sub-basin where it mixed with low ³⁴S BSR sulfide to form the massive and bedded sulfides. The REE patterns of sulfide layers and associated quartz albitite and baritite are similar to those of the host biotite quartz schists, suggesting that the hydrothermal fluids leached REE from the underlying rocks. Pb isotope ratios in galena form an array between the Upper Crust and the Mantle reservoir curves, which indicates that the lead is derived from upper crustal rocks comprising mafic igneous units. The Sr⁸⁷/Sr⁸⁶ ratio of 0.7101 for carbonate within the sulfide layers also suggests that Sr is derived from the mixing of Sr leached from upper crustal rocks with Middle Devonian seawater Sr. A Rb-Sr isochron age of 389.4 ± 6.4 Ma for sulfide layers and the interbedded hydrothermal sediments is consistent with the age of host Mid-Devonian strata. Ar³⁹/Ar⁴⁰ plateau age at 352.8 ± 3.5 Ma and Ar³⁹-Ar⁴⁰ isochron age of 346.6 ± 6.4 Ma for albite in the quartz albitite intercalated with sulfide layers indicate either albite formation after the sulfides or thermal resetting of the Rb-Sr system at about 350 Ma, the age of collision between the North China and Yangtze cratons.Editorial handling: E. Frimmel     

Sulfur isotope evidence for penetration of MVT fluids into igneous basement rocks,southeast Missouri,USA

Previous studies of galena and sphalerite from Paleozoic MVT deposits in the Viburnum Trend, southeast Missouri documented large variations in ³⁴S values throughout the ore-forming event. The present study of Cu-Fe-sulfides reveals a similar ³⁴S variation that reflects two end-member sulfur reservoirs whose relative importance varied both temporally and spatially. More ³⁴S-enriched sulfides (³⁴S approaching 25) indicate introduction of sulfur from basinal sedimentary sources, whereas more ³²S-enriched sulfides (³⁴S < 5) may reflect fluids moving through underlying granitic basement. Two areas containing Precambrian, igneous-hosted FeCu mineralization in southeast Missouri (West and Central Domes of Boss-Bixby) were investigated to elucidate their relationship to Cu-rich MVT orebodies hosted nearby within the overlying Cambrian Bonneterre Dolomite. Mineralization at Boss-Bixby is composed of an early phase of iron oxide deposition followed by Cu-Fe-sulfides. The Central Dome is faulted and its mineralization is more fracture-controlled than the typically podiform ores of the West Dome. The ³⁴S values of West Dome sulfides are 0.9 to 6.5 and pyrite-chalcopyrite indicate a temperature of 525° ± 50 °C. These data indicate an igneous source of sulfur during Precambrian ore deposition. In contrast, ³⁴S values of Central Dome sulfides are 9.4 to 20.0 and pyrite-chalcopyrite indicate temperatures of 275° ± 50 °C. Similar ³⁴S values are obtained for chalcopyrite from the overlying MVT deposits. We speculate that deeply circulating, basin-derived MVT fluids mobilized sulfur and copper from the underlying igneous basement and redeposited them in overlying Curich MVT orebodies, as well as overprinting earlier Precambrian sulfides of the Central Dome with a later, Paleozoic MVT sulfur isotope signature. Many models for MVT fluid circulation in the Midcontinent region of North America assume that igneous basement rocks are an impermeable boundary, but in southeast Missouri, evidence exists for structurally controlled MVT fluid movement > 600 m vertically through underlying Precambrian igneous rocks. Such basement involvement has been suggested for other carbonate-hosted base-metal districts (e.g. Irish base metal deposits) and should be considered an integral part of the ore-forming process in southeast Missouri.     

A sulfur isotopic study of alunites from Latium and Tuscany,central Italy

Sulfur isotope analyses were made on 14 alunites from volcanic and sedimentary rocks widely different in chemistry and age from southern Tuscany and northern Latium, central Italy. The ³⁴S values range from +0.7 to +9.6, and appear not to be related to the nature of the host rock. Geological and isotopic evidence suggests that all the alunites formed by supergenic oxidation of sulfides. Sulfides occurring with alunites in the volcanic rocks of Latium can be divided into an isotopically light group of probably magmatic origin (³⁴S=–1.5 to +3.4) and a heavy one with ³⁴S=+6.0 to +10.3, tentatively interpreted as deposited by hydrothermal fluids that leached sulfides of similar ³⁴S/³²S from the deep basement. Such an interpretation is consistent with recent studies indicating that in the perityrrhenian belt of Latium exists a continuation, at depth, of the Tuscan stratigraphic series, rich in sulfides with ³⁴ from +6 to +12.     

Apparent stable isotope heterogeneities in gangue carbonates of the Mississippi Valley-type Zn-Pb deposit of San Vicente,central Peru

The aim of the present communication is to emphasize that some variations of the measured ¹³C and ¹⁸O values are apparent, and due to analytical interferences caused by the presence of sulfur and organosulfur compounds in the analyzed carbonates. This is particularly relevant for isotopic studies on carbonate-hosted mineral deposits, where the nearly ubiquitous association of the host carbonates with organic matter and sulfides can certainly affect the metallogenetic interpretations. In this work two methods were used to overcome the disturbing effects of sulfides and organic matter: (1) sample pretreatment following the method proposed by Charef and Sheppard (1984), combining the oxidation of organic matter with sodium hypochlorite and trapping of the sulfur species with silver phosphate; and (2) laser-based microprobe extraction. Apparent isotopic variations in sparry dolomite from a single hand sample of zebra ore from the MVT Zn-Pb deposit, San Vicente, central Peru, are as large as 6 ¹³C and 4 ¹⁸O. These variations are reduced to several tenths of a per mil when the samples are pretreated. A careful examination of the effects of treatment with NaOCl and/or Ag₃PO₄ in relation to the concentration of sulfide inclusions indicates that the main disturbing effects for ¹³C values are the presence of sulfur species and organic matter, whereas the ¹⁸O values are mainly affected by the presence of sulfides. Fine- and medium-grained replacement carbonates from MVT and other sediment-hosted base metal deposits are potentially the most affected during isotope analysis, due to the common presence of organic matter and sulfides. Using in situ laser microprobe techniques, it is possible to determine isotopic variations at a sub-millimeter scale. Our results show that laser extraction analysis allows a more precise sampling of the carbonate minerals, and minimizes contamination of the sample with sulfides and to some extent with intergrown organic matter. However, there is an isotopic shift associated with the laser extraction technique, of the order of 0.5–1 for ¹³C and ¹⁸O values.     

Ammoniten-Ökologie am Beispiel des Oberjura

Zusammenfassung In vielen Fällen beeinflussen äußere Faktoren das Vorkommen der Ammoniten. Im Oberjura spielt die Wassertiefe eine große Rolle, daneben tritt die Wassertemperatur. Voraussetzungen der ökologischen Analyse sind bodenbezogenes Leben der Tiere und postmortale Autochthonie der Schalen. Methoden und Fehlerquellen werden besprochen. Aus der ökologischen Bindung vieler Ammoniten ergeben sich Folgen, vor allem für Stratigraphie, Phylogenie und Ontogenie.

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In many cases external factors determine the occurence of the ammonites. In the Upper Jurassic the depth of the sea is of great importance, as well as the temperature of the water. Ecological analysis requires life of the animals close to the sea floor, and that the shells are autochthonous.Methods and sources of errors are discussed. The dependence on environment of many ammonites has consequences, especially for stratigraphy, phylogeny and ontogeny.

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Résumé Souvent des facteurs extérieurs déterminent la présence des ammonites. Dans le Jurassique Supérieur la profondeur de la mer joue un grand rôle, aussi bien que la température de l'eau. L'analyse écologique doit supposer que les animaux vivent près du fond de la mer et que les coquilles sont autochtones. Les méthodes et les sources d'erreurs sont discutées. La dépendance des ammonites de leur milieu a des conséquences avant tout pour la stratigraphie, la phylogénie et l'ontogénie.

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Isotopic composition of oxygen and hydrogen in mud-volcanic waters from Taman (Russia) and Kakhetia (Eastern Georgia)

The ¹⁸O and D values in mud-volcanic waters of the Taman Peninsula and Kakhetia vary from +0.7 to +10.0 and from –37 to –13 , respectively. These values increase as the Greater Caucasus is approached. The increase in 18O and D also positively correlates with fluid generation temperatures based on hydrochemical geothermometers. This is accompanied by changes in the chemical composition of waters, in which contents of alkali metals, HCO^– ₃ ion, and boron increase, while the content of halogen ions (Cl, Br, J) decreases. Changes in the isotopic composition of water are also accompanied by the increase of ¹³ in methane and decrease of ¹¹ B in clays. Analysis of formal models of the evolution of isotopic composition of mud-volcanic waters showed that mud volcanoes are recharged by freshened water from the Maikop paleobasin with an inferred isotopic composition of D –40 and ¹⁸ O –6. Based on this assumption, the ¹⁸O and D values observed in mud-volcanic waters can be explained not only by processes of distillation and condensation in a closed system, but also by combined processes of isotopic reequilibration in the water-illite-methane system.Translated from Litologiya i Poleznye Iskopaemye, No. 2, 2005, pp. 143–158.Original Russian Text Copyright © 2005 by Lavrushin, Dubinina, Avdeenko.     

Schwefel-Isotopenuntersuchungen an der Blei-Zink-Erzlagerstätte Grund (Westharz,Bundesrepublik Deutschland)

Zusammenfassung Die S-Isotopenverteilung wurde an 67 Sulfid- und 17 Barytproben aus der Blei-Zink-Erzlagerstätte Grund untersucht. Die ³⁴S-Werte der Zinkblende der Mineralisationsphase II liegen im Westfeld-Erzmittel I und in den östlich anschließenden Erzmitteln zwischen +4 und +6, in dem am weitesten westlich liegenden Westfeld-Erzmittel II zwischen +6 und +10. Die Werte für Bleiglanz der Mineralisationsphase II sind +2 bis +4 bzw. +4 bis +7. Die Sulfide der Mineralisationsphase III haben allgemein niedrigere -Werte. Koexistierende Sulfide zeigen eine deutliche Fraktionierung, wobei stets _ZnS > _PbS ist; die Differenz beträgt in der Mineralisationsphase II im Mittel 1,8, in der Phase III 3. Dies deutet auf niedrigere Bildungstemperatur der Minerale der Phase III hin. Zur genetischen Deutung der beobachteten -Abnahme beim Übergang zur Mineralisationsphase II werden vier Modelle diskutiert. Baryte zeigen innerhalb der Lagerstätte recht einheitliche ³⁴S-Werte zwischen +11 und +14,5%. Diese Einheitlichkeit wird durch den Einfluß deszendenter Zechstein-Lösungen erklärt.

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³⁴S-values are given for 67 sulfide and 16 barite specimens from the Pb-Zn-deposit Grund (Harz mountains, W-Germany). In the central part of the deposit the sulfide 's of the first major mineralization (phase II) range from: ZnS +4 to +6 and PbS +2 to +4. The sulfides of the second major mineralization (phase III) are depleted in ³⁴S and range from: ZnS +2 to +4, PbS –1,4 to 3. The sulfides at the western end of the vein system are heavier; the phase II minerals ranging from: ZnS +6 to 10 and PbS +4 to 7. The mean -difference between co-existing ZnS and PbS in phase II is 1,8, in phase III 3. This indicates lowering of temperature of formation for the phase III ore. Four models have been set up in order to explain the observed -variation. Barites with rather uniform 's from +11 to +14,5 are probably affected by descendent solutions from overlying sulfate sediments of Permian age.

     

The isotopic constitution of sulphur in some stratiform lead-zinc sulphide ores

Sulphur isotope measurements on five Australian stratiform lead-zinc sulphide ores are presented. Each deposit is characterised by a conspicuously narrow spread of values, mean ³⁴S heavier than meteoritic, average crustal, and, where sampled stratigraphically, ³⁴S related to stratigraphy rather than propinquity. When considered with other deposits of the same class from elsewhere, several seemingly general features appear: Mean ³⁴S heavier than meteoritics; ranges for individual deposits narrow and rarely more than 8 with standard deviation approximately 1 to 2; individual values for the whole group spread between, but almost entirely restricted by, the values for meteoritic S and seawater SO₄ ^—; no age effect; no apparent relationship between ³⁴S and lead type; and, where investigated, a stratigraphical affiliation. While no positive interpretation of these features is made, it is suggested that the sulphur concerned has been derived neither from migrant hydro-thermal solutions nor from the H₂S of normal biological sulphate reduction in seawater.

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Zusammenfassung Es werden Meßergebnisse von fünf australischen geschichteten Blei-Zink-Sulfid-Lagerstätten mitgeteilt: Jedes Vorkommen ist durch einen bemerkenswert engen Schwankungsbereich der Werte, Mittelwert ³⁴S schwerer als meteoritischer Schwefel/Durchschnittswert aus der Erdkruste, gekennzeichnet. Wo die Proben in stratigraphischer Abfolge entnommen wurden, zeigt der Wert ³⁴S eine stärkere Affinität zur Stratigraphie als zu absoluter Entfernung der Muster. Vergleicht man diese Werte mit solchen von anderen Vorkommen der nämlichen Lagerstättengruppe, so liegen einige allgemeine Eigenheiten auf der Hand: Für einige Vorkommen ist der Mittelwert ³⁴S schwerer als meteoritischer Schwefel; für einzelne Lagerstätten ist der Bereich eng und überschreitet kaum mehr als 8 mit der Standardabweichung von ungefähr 1 bis 2; Einzelwerte für die gesamte Lagerstättengruppe fallen fast ausschließlich zwischen die Werte für meteoritischen Schwefel und SO₄ ^2–-Ionen im Meerwasser; es herrscht kein dem geologischen Alter zuzuschreibender Effekt; auch gibt es keine augenscheinliche Beziehung zwischen dem ³⁴S-Wert und dem Blei-Typ; in jenen Fällen aber, wo Untersuchungsergebnisse vorliegen, ist eine Beziehung der Werte zur Stratigraphie zu erkennen. Obwohl keine positive Interpretation dieser Phänomena angestellt wurde, wird die Vermutung geäußert, daß der betreffende sulfidische Schwefel weder von wandernden hydrothermalen Lösungen noch vom H₂S einer normalen biologischen Sulfatreduktion im Meerwasser abgeleitet werden kann.

     

Recherche des variations isotopiques naturelles du potassium: Résultats,perspectives et interprétation

Résumé Après mise au point d'une technique permettant la comparaison des rapports isotopiques de potassium extrait de roches variées, à mieux que 0,2% près, on a recherché les variations possibles de l'abondance des isotopes 39 et 41. Certains résultats obtenus sur des roches volcaniques semblent indiquer des variations réelles. Une hypothèse est proposée pour l'interprétation de ces résultats, basée sur des phénomènes de différenciation crustale.

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The relative abundance of 41 and 39 isotopes of potassium has been determined in various rocks. A brief account of experimental technique is given; the reproducibility of measurement is about 0.2%. Most samples do not show significant variations, except some volcanic rocks. A tentative interpretation of these results, based upon crustal differentiation, is given.

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Zusammenfassung Dieser Bericht gibt die Ergebnisse der Isotopenanalysen des Kaliums, die an etwa vierzig verschiedenen Felsen-Probenstücken ausgeführt wurden. Die experimentelle Technik wird hier kurz beschrieben. Die meisten Felsarten, bis auf einige vulkanische Felsen, zeigen keine bedeutenden Veränderungen. Es wird eine Interpretation der Ergebnisse vorgeschlagen, die auf der Theorie der chemischen Differenzierung der Erdkruste beruht.

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Oxygen isotopes in mantle related and geothermally altered magmatites of the Transhimalayan (Gangdese) ranges

In closed magma systems SiO₂ approximately measures differentiation progress and oxygen isotopes can seem to obey Rayleigh fractionation only as a consequence of the behaviour of SiO₂. The main role of ¹⁸O is as a sensitive indicator of contamination, either at the start of differentiation ( ¹⁸O_init) or as a proportion of fractionation in AFC. Plots of ¹⁸O vs SiO₂-allow to determine initial ¹⁸O values for different sequences for source comparison. For NBS-28=9.60, the ¹⁸O at 48% SiO₂-varies between a high 6.4 for Kiglapait (Kalamarides 1984), 5.9 for Transhimalaya, 5.8 for Hachijo-Jima (Matsuhisa 1979), 5.6 for Koloula (Chivas et al. 1982) and a low 5.3 for the Darran Complex, New Zealand. The Transhimalayan batholiths (Gangdese belt) were emplaced in the Ladakh-Lhasa terrane, between the present-day Banggong-Nujiang, and Indus-Yarlung Tsangbo suture zones, after its accretion to Eurasia. The gradient of the least contaminated continuous ( ¹⁸O vs SiO₂-igneous trend line is similar to that of Koloula, and AFC calculations suggest a low secondary assimilation rate of less than 0.05 times the rate of crystallisation. Outliers enriched in ¹⁸O are frequent in the Lhasa, and apparently rare in the Ladakh transsect. Low- ¹⁸O (5.0–0) granitoids and andesites on the Lhasa-Yangbajain axis are the result of present day or recent near-surface geothermal activity; their quartzes still trace the granitoids to the Transhimalaya ¹⁸O trend line, but the distribution of low total rock or feldspar ¹⁸O values could be a guide to more recent heat flow and thermally marked tectonic lineaments. Two ignimbrites from Maqiang show hardly any ¹⁸O-contamination by crustal material.     

Stable isotope (C,O, S) systematics of the mercury mineralization at Idrija,Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the ¹³C and ¹⁸O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the ¹³C and ¹⁸O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (¹³C–4 and ¹⁸O+10), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The ³⁴S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The ³⁴S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from –19.1 to +22.8, and from –22.4 to +59.6, respectively, suggesting mixing of sulfur from different sources. The peak of ³⁴S values of cinnabar and pyrite close to 0 is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the ³⁴S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive ³⁴S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates.Editorial handling: P. Lattanzi