Sulphur isotope patterns from the Bleiberg deposit (Eastern Alps) and their implications for genetically affiliated lead–zinc deposits

Summary A set of 354 sulphur isotope data from the Bleiberg deposit, the type deposit of Alpine low temperature carbonate hosted Pb–Zn deposits (APT deposits), is critically evaluated applying statistical methods. The sulphur isotope patterns vary significantly among the ore horizons. This suggests a long lasting and polyphase mineralisation system. The sulphur isotope composition of barite corresponds to that of Carnian seawater (i.e. 16 ³⁴S). The ³⁴S values of the iron sulphides correspond to data from sedimentary iron sulphides. Pb and Zn sulphides are characterized by three normally distributed ³⁴S populations with mean values of –6 to –8, –13 to –18, and –25 to –29. Heavy sulphur (>–10 ³⁴S) indicates contribution of sulphide sulphur from epigenetic-hydrothermal fluids, whereas light sulphide sulphur (<–21 ³⁴S) was produced by sulphur – reducing bacteria. The intermediate population is explained by mixing of sulphur derived from these two sources. Other sources of local importance, however, can not be excluded. The isotope populations correspond only partly to the paragenetic ore stages. The sulphur isotope patterns in the APT deposits are regionally different. Data from other low-temperature sediment-hosted Pb–Zn deposits support the proposed interpretation. A comparison demonstrates that the sulphur isotope patterns of APT deposits correspond to patterns of the Irish type deposits, but are different to those of Mississippi Valley type deposits.Supplementary material to this paper is available in electronic form at http://dx.doi.org/10.1007/s00710-004-0071-3     

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.

---

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.

     

Genetic aspects of the Geita and Jubilee Reef Archean BIF-hosted gold deposits,Tanzania

The Sukumaland Greenstone Belt (new name), which is located in north-western Tanzania hosts a large number of gold deposits, prospects and occurrences. The Archean stratigraphy comprises an older basement of granitic gneisses (Dodoman System) overlain by mafic and ultramafic volcanics which are succeeded by felsic volcanic rocks and a banded iron formation (BIF), predominantly as oxide facies. The volcanics and BIF together make up the Nyanzian System. The uppermost part of the Archean stratigraphy (Kavirondian System) consists of conglomerates and quartzites which rest unconformably on the older units. The sequence has been intruded by both syn- and post-orogenic granitoids and by several generations of felsic and intermediate dykes and sills. Gold mineralisation is abundant in all stratigraphic units except for the granitic rocks. Six types of mineralisation can be distinguished. These are BIF-hosted, hear zone type, (quartz-) vein type, clastic sedimenthosted alluvial/eluvial, and massive sulphide type deposits. The last is represented by only one deposit in this area.The location of the BIF-hosted gold mineralisation is controlled by trachytic rocks of both dyke- and sill-like appearance and brecciated shear zones which follow the contacts between BIF and intercalations of tuff. The host rocks around these trachytes and shear zones have been pervasively mineralised with pyrite, auriferous pyrite and native gold, selectively replacing magnetite layers.The mineralisation grades from massively replaced layers at the trachyte/BIF- or tuff/BIF-contact into disseminated layers, rare specks of pyrite and eventually into barren BIF. Permeable features such as veins, fractures, breccia zones and shear zones may contain mineralisation even away from the main ore zones.Ore textures and fire assay results from Geita and Jubilee Reef indicate the introduction of ore fluids via epigenetic conduits into the adjacent wall rocks. Neither a depletion halo in the adjacent BIF (lateral secretion) nor a zone of footwall alteration or stringer ore, which might support a syngenetic/replacement concept for the mineralisation have been found.The main precipitating mechanism was probably a redox reaction of the ascending, reducing ore fluids with the magnetite of the BIF. This reaction resulted in the replacement of magnetite by pyrite, a rise in Eh, and the precipitation of gold together with the pyrite. The authors propose an epigenetic mineralisation process which produced ore-grade mineralisation of different styles in all stratigraphic units. The special physico-chemical trap of the magnetite layers led to the development of pyrite/gold mineralisation of generally stratabound appearance. The ore fluids originated probably from granitic intrusions and the underlying mafic volcanics are a possible gold source. For textural reasons the surrounding BIF is unlikely to have supplied a major portion of the gold.

---

Zusammenfassung Der Sukumaland Greenstone Belt (neuer Name) im Nordwesten Tanzanias beherbergt eine große Zahl von Goldvorkommen unterschiedlicher wirtschaftlicher Bedeutung. Die Archaische Stratigraphie umfaßt ein aus granitischem Gneiss bestehendes Grundgebirge (Dodoman-System), auf dem mafische und ultramafische Vulkanite ruhen, die wiederum von felsischen Vulkaniten und hauptsächlich oxydischer banded iron formation (BIF) überlagert werden. Diese Vulkanit- und BIF-Serien stellen die stratigraphische Einheit des Nyanzian-Systems dar. Der Top der Archaischen Stratigraphie wird von Konglomeraten und Quarziten des Kavirondian gebildet, welches diskordant auf den älteren Einheiten liegen. Synund postorogene Granitoide sowie mehrere Generationen von felsischen und intermediären Gängen sind in die Archaische Abfolge intrudiert.Goldindikationen und -vorkommen sind relativ häufig und treten in allen stratigraphischen Einheiten mit Ausnahme der Granitoide auf. Dabei lassen sich sechs Typen von Goldmineralisationen unterscheiden; diese sind: Gold in BIF, in Scherzonen, in Goldquarzgängen, in klastischen Archaischen Sedimenten, in Alluvionen und in massiven Sulfiden. Vom letztgenannten Typ ist bisher lediglich ein Vorkommen im Untersuchungsgebiet bekannt. Die Position der Goldmineralisation in den BIFs wird von trachitischen Dykes und Sills sowie von Scherzonen im Kontaktbereich zwischen BIF und Tuffeinschaltungen kontrolliert. Die Kontaktbereiche zu den brekziierten Scherzonen und trachytischen Gesteinen sind stark mineralisiert, wobei Pyrit, goldhaltiger Pyrit und Freigold selektiv Magnetitlagen verdrängt und sulfidisiert haben.Der Verdrängungsprozeß Magnetit/Pyrit hat im direkten Kontaktbereich zwischen Trachit bzw. Tuffzwischenlagen und BIF zur Bildung von massiven Pyrit-Lagen geführt. Lateral gehen diese massiv sulfidisierten Bereiche in Lagen von Magnetit mit disseminierter Pyritmineralisation über, weiter distal in vereinzelte Pyritkörner und schließlich in sulphidfreie Oxydfazies-BIF. Außerhalb dieser mineralisierten Kon taktzonen, teilweise in erheblichem Abstand zur Hauptmineralisation, enthalten auch Bereiche erhöhter (tektonischer) Permeabilität, wie z. B. kleine Trümer, Klüfte, Brekzien- und Scherzonen, stellenweise reiche Pyrit/Gold-Mineralisationen.Untersuchungen von Erzverteilung und -texturen sowie Goldanalysen (fire assay) von Geita und Jubilee Reef belegen eine Wanderung der Erzlösungen durch epigenetische Strukturen in die Magnetitlagen des umgebenden Gesteins. Es konnten weder Zeichen für Lateralsekretion — vom umliegenden Gestein in Erzzonen oder Goldquarzgänge — noch eine Alterationszone im stratigraphisch Liegenden festgestellt werden; beide Phänomene wären deutliche Argumente für ein syngenetisches Konzept (mit teilweiser späterer Umverteilung der Mineralisation). Die Verteilungsmuster der Goldgehalte sprechen gegen eine intraformationelle Herkunft des Goldes.Der Hauptausfällungsmechanismus dürfte eine Redoxreaktion der aufsteigenden reduzierten Erzlösungen mit den Magnetitlagen der BIF gewesen sein. Diese Redoxreaktion hatte die Verdrängung des Magnetit durch Pyrit (Sulfidisierung) sowie eine drastische Erhöhung des Eh-Wertes zur Folge und bedingte so die Ausfällung des Goldes zusammen mit dem Pyrit.Ein epigenetischer Mineralisationsprozeß führte zur Bildung reicher Goldvererzungen unterschiedlicher Typen in sämtlichen stratigraphischen Einheiten. Innerhalb der BIF bedingte die spezielle physiko-chemische Falle der Magnetitlagen die Bildung schichtgebundener Pyrit/Goldmineralisation epigenetischen Ursprungs. Die Erzlösungen stammten vermutlich von granitischen Intrusionen wobei die mafischen Vulkanite des tieferen Nyanzian als naheliegende Lieferanten des Goldes in Betracht kommen.

---

Résumé Le «Sukumaland Greenstone Belt» (nouveau nom), situé dans le nord-ouest de la Tanzanie, renferme un grand nombre de venues aurifères, d'importances économiques diverses. Au point de vue stratigraphique, l'Archéen comprend un socle ancien de gneiss granitiques (Système de Dodoman), surmonté de volcanites mafiques à ultramafiques auxquelles succèdent des volcanites felsitiques et une formation ferrugineuse rubanée (BIF = banded iron formation) de faciès essentiellement oxydé. L'ensemble des volcanites de la BIF constitue le Système Nyanzien. La partie supérieure de l'Archéen (Système Kavirondien) consiste en conglomérats et quartzites discordants sur les unités plus anciennes. Le tout a été intrudé par des granitoïdes syn- et post-orogéniques et par plusieurs générations de dykes et sills felsitiques et intermédiaires. La minéralisation en or est abondante dans toutes les unités stratigraphiques, à l'exception des roches granitiques. On peut distinguer six types de minéralisations: celles qui sont contenues dans la BIF, celles qui sont associées à des shear-zones, à des veines de quartz, des paléo-placers, des minéralisations alluviales et éluviales et un type à sulfures massifs, ce dernier représenté seulement par un seul exemplaire.L'emplacement des minéralisations contenues dans la BIF est en relation avec la présence de roches trachytiques en sills ou en dykes et avec des shear-zones bréchiées qui jalonnent le contact entre la BIF et des intercalations de tuf. Les rocheshôtes au voisinage de ces trachytes et de ces shear-zones ont été imprégnées de pyrite, de pyrite aurifère et d'or natif, qui ont remplacé sélectivement les lits de magnétite. Il existe tous les intermédiaires entre les lits remplacés massivement aux contacts trachyte/BIF ou tuf/BIF, les lits à pyrites éparses et les lits stériles. En dehors, et même assez loin de ces zones de contact favorables, des concentrations minéralisées se rencontrent en des endroits perméables, tels que veines, fractures, zones bréchiques et shear-zones.Les textures des minerais ainsi que les analyses (fire assay) du «Geita and Jubilee reef» montrent l'envahissement des roches adjacentes par des solutions minéralisantes circulant dans des conduits épigénétiques. On n'a observé ni halos appauvris dans les roches BIF adjacentes, ni zones d'altération dans les roches stratigraphiquement sous-jacentes, phénomènes susceptibles d'être invoqués à l'appui d'un modèle de remplacement syngénétique.Le mécanisme principal de la précipitation a probablement consisté en une réaction d'oxydo-réduction entre la magnétite de la BIF et les fluides minéralisés réducteurs ascendants. Cette réaction a entraîné le remplacement de la magnétite par la pyrite, une augmentation de Eh et la précipitation simultanée de l'or. Les auteurs proposent un processus de minéralisation épigénétique aboutissant à des dépôts de types divers dans chaque unité stratigraphique. Les pièges physico-chimiques que constituaient les niveaux à magnétite ont conduit à des corps minéralisés de pyrite aurifère d'allure généralement stratiforme. L'origine des fluides minéralisateurs aurifères doit probablement être trouvée dans les intrusions granitiques et les volcanites mafiques sous-jacentes. Des raisons structurales rendent peu probable qu'une fraction importante de l'or provienne de la BIF avoisinante.

---

Sukumaland'a . , — —, , , . . (BIF). Nyanzian. Kavirondian. . - - , . . 6 : BIF, , , , . . BIF , — . , , . BIF . - , — , , BIF. , , , .: , , , / . , — fire assay — Geita Jubilee . , , . , . . . . , . . BIF - / . , , ; Nyanzian , .

     

Oxygen isotope geochemistry of the Mesozoic volcanics of the Etendeka Formation,Namibia

The Etendeka Formation volcanics consist of a bimodal association of basalts and quartz latites. Forty three new whole rock oxygen isotope analyses are reported for all the major magma types. All the rocks except a minor suite of dolerites have higher ¹⁸O values than normal mantle. The basic rocks (average of 29=8.8) have significantly different ¹⁸O to the acid rocks (average of 10=14.4) These data are apparently consistent with previously published petrogenetic models, which propose that the basalts were affected by crustal contamination and that the quartz latites are crustally derived. However, mineral oxygen data show that there is significant oxygen isotopic disequilibrium between phenocryst and whole rock, the latter being significantly higher in most cases. One of the basic magma types (the Tafelberg basalts) shows mutual positive correlations between ¹⁸O, SiO₂ and _Sr. If these correlations are due to crustal contamination, then as much as 45% contamination is required by material having a ¹⁸O value of 15 which is the maximum observed value in the Damaran basement rocks. In the absence of pyroxene phenocryst ¹⁸O data for the high _Sr Tafelberg basalts (they are aphyric), it is not possible to confirm that contamination has taken place. An alternative explanation is that the correlation between _Sr and SiO₂ resulted from assimilation coupled with fractional crystallization (AFC) (before emplacement). Post-eruption alteration resulted in a correlation between SiO₂ ¹⁸O because the material with the most Si-O bonds was able to concentrate ¹⁸O more effectively. The limited mineral data for the quartz latites suggests that there is some source heterogeneity. A pyroxene ¹⁸O value of 10% for a southern Etendeka quartz latite is consistent with a crustal source.     

Oxygen isotope geochemistry of pyroclastic clinopyroxene monitors carbonate contributions to Roman-type ultrapotassic magmas

The oxygen isotope geochemistry and chemical composition of clinopyroxene crystals from Alban Hills pyroclastic deposits constrain the petrological evolution of ultrapotassic Roman-type rocks. Volcanic eruptions in the 560–35 ka time interval produced thick pyroclastic deposits bearing clinopyroxene phenocrysts with recurrent chemical characteristics. Clinopyroxenes vary from Si–Mg-rich to Al–Fe-rich with no compositional break, indicating that they were derived from a continuous process of crystal fractionation. Based on the ¹⁸O and trace element data no primitive samples were recovered: monomineralic clinopyroxene cumulates set the oxygen isotope composition of primary magmas in the range of uncontaminated mantle rocks (5.5), but their REE composition resulted from extensive crystal fractionation. Departing from these mantle-like ¹⁸O_Cpx values the effects of crustal contamination of clinopyroxene O-isotope composition were identified and used to monitor chemical variations in the parental magma. ¹⁸O values in Si–Mg-rich clinopyroxene are slightly higher than typical mantle values (5.9–6.2), and the low REE contents are representative of early stages of magmatic differentiation. ¹⁸O values as high as 8.2 are associated with Al–Fe³⁺-rich clinopyroxene showing high REE contents. These ¹⁸O values are characteristic of crystals formed during the late magmatic stages of each main eruptive phase. Geochemical modelling of ¹⁸O values vs. trace element contents indicates that these ultrapotassic magmas were derived from fractional crystallization plus assimilation of limited amounts of carbonate wall rocks starting from a primary melt, and from interaction with CO₂ derived from country rocks during crystal fractionation.     

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.     

Sea water basalt interaction in spilites from the Iberian Pyrite Belt

Low grade hydrothermally metamorphosed mafic rocks from the Iberian Pyrite Belt are enriched in ¹⁸O relative to the oxygen isotopic ratio of fresh basalt (+6.5±1). The observed ¹⁸O whole rock values range from +0.87 to +15.71 corresponding to positive isotopic shifts of +5 to +10, thus requiring isotopic exchange with fluids under conditions of high water:rock ratios at low temperatures. The lowest ¹⁸O observed corresponds to an albitized dolerite still and is compatible with independent geochemical data suggesting lower water: rock ratios for the alteration of these rocks.The isotope data are consistent with the hypothesis that the spilites from the Pyrite Belt were produced by interaction of basaltic material with sea water.Significant leaching of transition metals from the mafic rocks during alteration coupled with available sulphur isotopic data for the sulphide ores also suggest that sea water may have played an important role in the formation of ore deposits in the Iberian Pyrite Belt.     

Stable isotope geochemistry of the Archean Val-d‘Or (Canada) orogenic gold vein field

A systematic study of the auriferous quartz veins of the Val-dOr vein field, Abitibi, Quebec, Canada, demonstrates that the C, O, S isotope composition of silicate, carbonate, borate, oxide, tungstate and sulphide minerals have a range in composition comparable to that previously determined for the whole Superior Province. The oxygen isotope composition of quartz from early quartz–carbonate auriferous veins ranges from 9.4 to 14.4 whereas later quartz-tourmaline-carbonate veins have ¹⁸O_quartz values ranging from 9.2 to 13.8 . Quartz-carbonate veins have carbonate (¹⁸O: 6.9–12.5 ; ¹³C: –6.2– –1.9 ) and pyrite (³⁴S: 1.2 and 1.9 ) isotope compositions comparable to those of quartz-tourmaline-carbonate veins (¹⁸O: 7.9–11.7 ; ¹³C: –8.0 – –2.4 ; ³⁴S: 0.6–6.0 ). ¹⁸O_quartz values in quartz-tourmaline-carbonate veins have a variance comparable to analytical uncertainty at the scale of one locality, irrespective of the type of structure, the texture of the quartz or its position along strike, across strike or down-dip a vein. In contrast, the oxygen isotope composition of quartz in quartz-tourmaline-carbonate veins displays a regional distribution with higher ¹⁸O values in the south-central part of the vein field near the Cadillac Tectonic Zone, and which ¹⁸O values decrease regularly towards the north. Another zone of high ¹⁸O values in the northeast corner of the region and along the trace of the Senneville Fault is separated by a valley of lower ¹⁸O values from the higher values near the Cadillac Tectonic Zone. Oxygen isotope isopleths cut across lithological contacts and tectonic structures. This regional pattern in quartz-tourmaline-carbonate veins is interpreted to be a product of reaction with country rocks and mixing between (1) a deep-seated hydrothermal fluid of metamorphic origin with minimum ¹⁸O=8.5 , ¹³C=0.6 and ³⁴S=–0.4 , and (2) a supracrustal fluid, most likely Archean seawater with a long history of water-rock exchange and with maximum ¹⁸O=3.9 , ¹³ C=–5.6 and ³⁴S=5.0 .     

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     

Stable isotope and fluid inclusion studies of carbonate deposits from the Tolfa Mountains mining district (Latium,central Italy)

Carbon and oxygen isotope analyses were made of representative samples of calcite and quartz from the carbonate deposits in the Tolfa Mountains mining district. Measurements were also made of hydrogen isotope compositions, filling temperatures and salinities of fluid inclusions in these minerals. There are three stages of mineralization at Tolfa. In stage I, characterized by calc-silicate hornfels, the carbonates have relatively high ¹⁸O values of 14.5 to 21.6 suggesting a rather low water/rock ratio. ¹³C values of –0.3 to 2.1 indicate that appreciable decarbonation or introduction of deep-seated carbon did not occur. Stage II is marked by phanerocrystalline carbonates; ¹⁸O values of 13.1 to 20.0 and ¹³C values of 0.7 to 5.0 identify them as hydrothermal veins rather than marbles. D values of –56 to –50 for inclusion fluids suggest a possible magmatic component to the hydrothermal fluid. Filling temperatures of coarse-grained samples of Calcite II are 309° to 362° C with a salinity range of 5.3 to 7.1 weight percent NaCl. Calculated ¹⁸O values of 11–12 for these fluids are again indicative of low water/rock ratios. The sparry calcites of stage III have ¹⁸O and ¹³C values of 8.1 to 12.9 and –1.7 to 3.2, respectively. D values of inclusion fluids are –40 to –33, clearly heavier than in earlier stages and similar to values of modern local ground waters. A salinity measurement of <0.1 weight percent NaCl in a sample of Calcite III is compatible with a relatively unaltered ground water origin for this fluid. Precipitation of the sparry calcite took place at much lower temperatures, around 160° C. For quartz, ¹⁸O values of 9.3 to 12.4 and D values for inclusions of –53 to –28 are consistent with its late occurrence and paragenetic link with associated carbonates.     

The Hiendelaencina epithermal silver-base metal district,Central Spain: Tectonic and mineralizing processes

The northeastern sector of the Spanish Central System hosts important Stephanian-Permian silver-base metal epithermal mineralizations defining the so-called Hiendelaencina District. The overall geotectonic evolution of this region indicates a major late Variscan extensional period involving the unroofing of dome-shaped metamorphic core complexes, which ultimately led to the radial brittle disruption of these bodies allowing the ascent of andesitic magmas and high-level hydrothermal activity. The deposits are hosted by high-grade metaphorphic rocks belonging to these complexes. Mineralogical and fluid inclusion studies reveal that the mineralizations were formed during two to four hydrothermal stages. These are the result of complex interactions between fluids of contrasted temperatures and salinities. Data on sulphur isotopes suggest that two sources of sulphur existed: magmatic (andesitic derived, with ³⁴S + 6) and metasediment-derived (with initial ³⁴S probably + 25).     

Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

---

Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

A stable isotope study of retrograde alteration in SW Connemara,Ireland

Dalradian metamorphic rocks, Lower Ordovician meta-igneous rocks (MGS) and Caledonian granites of the Connemara complex in SW Connemara all show intense retrograde alteration. Alteration primarily involves sericitization and saussuritization of plagioclase, the alteration of biotite and hornblende to chlorite and the formation of secondary epidote. The alteration is associated with sealed microcracks in all rocks and planes of secondary fluid inclusions in quartz where it occurs, and was the result of a phase of fluid influx into these rocks. In hand specimen K-feldspar becomes progressively reddened with increasing alteration. Mineralogical alteration in the MGS and Caledonian granites took place at temperatures 275±15°C and in the MGS P_fluid is estimated to be 1.5 kbar during alteration. The °D values of alteration phases are:-18 to-29 (fluid inclusions),-47 to-61 (chlorites) and-11 to-31 (epidotes). Chlorite ¹⁸O values are +0.2 to +4.3, while ¹⁸O values for quartz-K-feldspar pairs show both positively sloped (MGS) and highly unusual negatively sloped (Caledonian granites) arrays, diverging from the normal magmatic field on a - plot. The stable isotope data show that the fluid that caused retrogression continued to be present in most rocks until temperatures fell to 200–140°C. The retrograde fluid had D -20 to-30 in all lithologies, but the fluid ¹⁸O varied both spatially and temporally within the range-4 to +7. The fO₂ of the fluid that deposited the epidotes in the MGS varied with its ¹⁸O value, with the most ¹⁸O-depleted fluid being the most oxidizing. The D values, together with low (<0) ¹⁸O values for the retrograde fluid in some lithologies indicate that this fluid was of meteoric origin. This meteoric fluid was probably responsible for the alteration in all lithologies during a single phase of fluid infiltration. The variation in retrograde fluid ¹⁸O values is attributed to the effects of variable oxygen isotope shifting of this meteoric fluid by fluid-rock interaction. Infiltration of meteoric fluid into this area was most likely accomplished by convection of pore fluids around the heat anomaly of the Galway granite soon after intrusion at 400 Ma. However convective circulation of meteoric water and mineralogical alteration could possible have occurred considerably later.     

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 constraints on the origin and depth of penetration of hydrothermal fluids associated with Hercynian regional metamorphism and crustal anatexis in the Pyrenees

Late Carboniferous (Hercynian) tectonism in the Pyrenees generated extremely steep thermal gradients at 8–14 km depth in the continental crust, producing andalusite- and sillimanite-grade metamorphism and partial melting of Lower Paleozoic metasediments under water-rich conditions. At the same time, amphibolite- and granulitefacies basal gneisses were equilibrated under dryer conditions at pressures of 4 to 7 kbar (14–25 km depth), beneath these higher-level rocks. We present 95 new oxygen isotopic analyses of samples from the Agly, St. Barthelemy, Castillon and Trois Seigneurs Massifs, highlighting contrasting ¹⁸O/¹⁶O systematics at different structural levels in the Hercynian crust, here termed Zones 1, 2, and 3. The unmetamorphosed, fossiliferous, Paleozoic shales and carbonates of Zone 1 have typical sedimentary ¹⁸O values, mostly in the range +14 to +16 for the pelitic rocks and +20 to +25 for the carbonates. The metamorphosed equivalents of these rocks in Zone 2 all have strikingly uniform and much lower ¹⁸O values; the metapelites mostly have ¹⁸O=+10 to +12, and interlayered metacarbonates from the Trois Seigneurs Massif have ¹⁸O of about +12 to +14. Typically, the Zone 3 basal gneisses are isotopically heterogeneous with variable ¹⁸O values ranging from +6 in mafic lithologies to +22 in carbonate-rich lithologies. Steep gradients in ¹⁸O (as much as 10 per mil over a few cm) are preserved at the margins of some metacarbonate layers. These data indicate that the Zone 3 gneisses were infiltrated by much smaller volumes of metamorphic pore fluids than were the overlying Zone 2 rocks, and that circulation of surface-derived H₂O (either seawater or formation waters, as evidenced by high D values) was mainly confined to the Paleozoic supracrustal sedimentary pile. This is compatible with an overall reduction of interconnected porosity with increasing depth, but perhaps even more important, the extensive partial melting at the base of Zone 2 may have produced a ductile, impermeable barrier to downward fluid penetration.Contribution No. 4287, Publication of the Division of Geological and Planetary Sciences, California Institute of Technology     

Sulphur isotopes in Lower Proterozoic iron and sulphide ores in northern Sweden

The present investigation deals with sulphur isotope distribution in Lower Proterozoic iron and sulphide mineralizations in northern Sweden. The contrasting sulphur isotope patterns are indicative of different genesis. Some 267 sulphur isotope analyses of pyrite, pyrrhotite, chalcopyrite, sphalerite, galena and bornite from 23 occurrences have been performed. Some deposits exhibit uniform compositions, although the mean ³⁴S values are clearly different, while other mineralizations have widely fluctuating values.The ³⁴S values in syngenetic, exhalative sedimentary skarn iron ores, quartz-banded iron ores and sulphide mineralizations of the 2.0–2.5 Ga old (Lapponian) Greenstone group show a large spread, supporting the existence of bacteriogenic sulphate reduction processes. The spread of the sulphur isotope values ( ³⁴S = -8 to +25), and the non-equilibrium conditions, point to a biogenic rather than to an inorganic reduction of seawater sulphate.The isotopic composition of the sulphides in the epigenetic Lannavaara iron ores which were formed by a hydrothermal scapolite-tourmalme-related process, indicates a sulphur source similar to that of the Greenstone group. The ³⁴S values of Cu-(Au) sulphide mineralizations in the Malmberget region (e.g. Aitik), which were formed by a similar process and hosted by the volcanics-volcanoclastics of the 1.9 Ga old Porphyry group, are slightly below zero , indicating a magmatic origin. The existence of different sulphur compositions for these mineralization types formed by a similar hydrothermal process, probably reflects the influence of the host rock, the solutions leaching pre-existing sulphides.In southern Norrbotten, epigenetic, Cu-Zn-Pb veintype mineralizations in metavolcanics and metasediments have ³⁴S values close to zero indicating a magmatic origin. The sulphur isotope data of the volcanogenic, massive sulphide ores of the Skellefte district, in particular the ores of the Adak dome, are close to zero .The lead and sulphur isotopic features of the sulphides in northern Sweden show that the ore-forming processes were of a different nature on both sides of the Archean-Proterozoic border, implying differences in the crustal development. Lead isotopes show that lead was mobilized from specific sources on each side of the border. The sulphur of the sulphides in the Greenstone group in NE Sweden and Finland was introduced by sedimentary processes, whereas the sulphur of the sulphide occurrences towards the SW, mainly in the Porphyry group, is dominated by a magmatic sulphur component.     

Metamorphic ore remobilization in the Hällefors district, Bergslagen, Sweden: constraints from mineralogical and small-scale sulphur isotope studies

The marble- and metavolcanic-hosted Pb–Zn–(Ag–Sb–As) deposits of the Hällefors district, located in the Palaeoproterozoic Bergslagen ore province, south central Sweden, comprise both stratabound sulphides and discordant, Ag-rich sulphide–sulphosalt veins. The complex sulphide–sulphosalt assemblages of the Alfrida-Jan Olof mines at Hällefors were investigated by a combination of ore microscopy, electron-microprobe analysis, and in situ laser sulphur isotope analysis. The massive ore is characterized by positive and homogeneous ³⁴S (+1.4 to +2.7 V-CDT), whereas vein-hosted sulphides and sulphosalts exhibit similar, but generally less positive to slightly negative ³⁴S (–0.6 to +2.0). Comparison of the observed ore mineral assemblages with calculated phase equilibria in the system Fe–As–S–O–H and isotopic fractionation as a function of temperature, oxygen fugacity and pH indicates that the vein-type mineralization was formed from relatively reduced and rather alkaline hydrothermal fluids. At these reduced conditions, fractionation of ³⁴S via changes of fO₂ is insignificant, and thus the isotopic signatures of the vein minerals directly reflect the composition of the sulphur source. We therefore conclude that the vein-type ore essentially inherited the sulphur isotope signature from the pre-existing massive sulphides via metamorphic remobilization at approximately 300–400°C and 2–3 kbar. Scales of remobilization observable are on the order of about 5 mm to 30 cm. Overall, the sulphide–sulphosalt assemblages from the Alfrida-Jan Olof mines exhibit ³⁴S values which are comparable to a majority of metasupracrustal-hosted deposits in the Bergslagen province, thereby suggesting a common origin from ca. 1.90–1.88 Ga volcanic-hydrothermal processes.Editorial handling: S. Nicolescu     

Fluid venting activity on the Costa Rica margin: new results from authigenic carbonates

Carbonate precipitates on mounds and along tectonic scarps off the Costa Rica margin are manifestations of subduction-induced dewatering. The long-term dewatering history is recorded in mineralogical, petrological and isotope signals of carbonates recovered from these sites. The carbonates are strongly depleted in ¹³C (–11 to –53 PDB) and enriched in ¹⁸O (+4 to +8 PDB). Thermogenic methane and biogenic methane were identified as sources of the carbon. Chemoherm carbonates and seepage-associated carbonates formed in a focused flow regime have lighter ¹³C values, while others formed in a more diffusive flow regime have slightly enriched C isotope values. Three fluid components were inferred based on the calculation of equilibrium ¹⁸O: clay dehydration water, gas hydrate water and seawater. Calculated equilibrium ¹⁸O values of carbonates from different down-core depths as well as from different precipitation stages show that the ¹⁸O of the precipitating fluid is progressively depleted with time. Dolostones showing a methane-C source and a well constrained O-isotope signature are thought to have formed at depth in the sediment and subsequently became exhumed. Glauconitic sandstones cemented by methane-derived carbonate provide evidence that fluid and solid material have been expelled by the mud volcano.     

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.

---

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.

     

Oxygen,sulfur, and strontium isotope and fluid inclusion studies of barite deposits from the Iglesiente-Sulcis mining district,Southwestern Sardinia,Italy

This paper deals with barite from stratiform, karst, and vein deposits hosted within Lower Paleozoic rocks of the Iglesiente-Sulcis mining district in southwestern Sardinia. For comparison sulfates from mine waters are studied. Stratiform barite displays ³⁴S=28.8–32.1, ¹⁸O=12.7–15.6, and ⁸⁷Sr/⁸⁶Sr=0.7087, in keeping with an essentially Cambrian marine origin of both sulfate and strontium. Epigenetic barite from post-Hercynian karst and vein deposits is indistinguishable for both sulfur and oxygen isotopes with ³⁴S=15.3–26.4 and ¹⁸O=6.6–12.5; ⁸⁷Sr/⁸⁶Sr ratios vary 0.7094–0.7140. These results and the microthermometric and salinity data from fluid inclusions concur in suggesting that barite formed at the site of mineralization by oxidation of reduced sulfur from Cambrian-Ordovician sulfide ores in warm, sometimes hot solutions consisting of dilute water and saline brine with different ¹⁸O values. The relative proportion of the two types of water may have largely varied within a given deposit during the mineralization. In the karst barite Sr was essentially provided by carbonate host rocks, whereas both carbonate and Lower Paleozoic shale host rocks should have been important sources for Sr of the vein barite. Finally, ³⁴S data of dissolved sulfate provide further support for the mixed seawater-meteoric water composition of mine waters from the Iglesiente area.