Isotopic Composition of Oxygen and Carbon and Formation Temperature of Accessory Minerals from Evaporitic Sediments in the Pripyat Trough

The isotopic composition of oxygen and carbon was studied in accessory carbonates and quartz separated from salts in Upper Devonian halogenous formations of the Pripyat Trough (Belorus). It is established that isotopic characteristics vary in a wide range. Values of ¹⁸O vary in the following range (SMOW): from 18.2 to 29.2 in calcites, from 15.7 to 32.5 in dolomites, and from 17.4 to 27.2 in quartz. Values of ¹³C range from –13.4 to 1.4 in calcites and from –11.1 to 1.7 in dolomites (PDB). Results obtained indicate highly variable isotope-geochemical conditions of sedimentation and early diagenesis during the formation of evaporitic sediments. Accessory minerals were repeatedly formed in a wide temperature range and probably at various stages of the lithogenesis.     

A stable isotope study of the Palaeoproterozoic Tallberg porphyry-type deposit,northern Sweden

The Tallberg deposit is situated in the Skellefte District in northern Sweden. It is a Palaeoproterozoic equivalent of Phanerozoic poryphyry-type deposits. The mineralization is situated within the Jörn granitoid complex and is associated with intrusive quartz-feldspar porphyries. The granitoids are coeval with mainly felsic volcanic rocks hosting several massive sulphide deposits. The alteration is generally of a mixed phyllic-propylitic type, but areas or zones associated with high gold grades exhibit phyllic alteration. Ore minerals are pyrite, chalcopyrite, sphalerite, magnetite, and trace amounts of molybdenite. In this stable isotope study, quartz, sericite, and chlorite from the alteration zones were sampled. The magmatic quartz has a ¹⁸O composition of + 6.2 to +6.7 whereas the quartz in the hydrothermal alteration zones have values ranging from +7.5 to +10.6. The calculated temperatures for this fractionation range from 430° to 520°C. The sericites have ¹⁸O ranging from +4.6 to +8.2 (average +6.6) and D -31 to -54 (average -41). Chlorites range from ¹⁸O +4.2 to +7.7 and D from –34 to –44. The range of ³⁴S of 11 pyrite samples is +3.8 to +5.5 with an average of +4.6 ± 0.5, suggesting a relatively homogeneous sulphur source, probably of magmatic origin. Modelling waters in equilibrium with the minerals indicates early magmatic fluids with ¹⁸O of 6.5. This fluid mixed with a low ¹⁸O and high D fluid, which is tentatively identified as seawater. The ¹⁸O signature of sericite and chlorite also indicates significant water-rock exchange, explaining the positive ¹⁸O values for the waters in equilibrium with the hydrated minerals.     

Deep crustal oxygen isotope variations: the Wawa-Kapuskasing crustal transect,Ontario

We have studied the oxygen isotopic composition of rocks from a 100 km transect through the central Superior province of Ontario, representing progressively the shallower terrains of the Kapuskasing structural zone (KSZ), the Wawa gneiss terrane (WGT), and the Michipicoten greenstone belt (MGB). These rocks range in age from 2.76 to 2.60 Ga, and correspond to a section through approximately 20 km of crustal thickness. Equivalent lithologic types have similar range of ¹⁸O values at each crustal level: tonalitic to granodioritic rocks: 6.4 to 9.5; dioritic and anorthositic rocks: 5.5 to 7.6; mafic gneisses: group 1 (majority): 5.7 to 7.1; group 2: 8.1 to 9.5. ¹⁸O values exhibit a remarkable correlation with SiO₂ values, similar to that observed in unaltered plutonic rocks of equivalent composition. Paragneisses have significantly higher ¹⁸O values: 9.3 to 12.2. Low-grade metavolcanic and metasedimentary rocks of the MGB are ¹⁸O-enriched compared to their high-grade equivalents in the KSZ and WGT: 7.4 to 13.3 for mafic to felsic metavolcanic rocks; 11.4 to 14.7 for clastic metasediments. Coexisting minerals exhibit ¹⁸O-fractionation consistent with equilibrium, but corresponding to uniform isotopic temperatures about 553 to 584°C across the entire transect, lower than the inferred metamorphic temperatures in the highest-grade (KSZ) terrane. The lack of distinctive isotopic differences between equivalent rock types in the KSZ, WGT and MGB suggests that there is no significant gradient in ¹⁸O with depth in the crust. The majority of mafic gneisses (group 1) appear to have been emplaced either as subaerial extrusives, intrusive sills, or, less likely, as submarine extrusives that were hydrothermally altered at high temperatures. The less abundant group 2 mafic rocks have the ¹⁸O values typical of greenstones that were altered at low temperature by seawater, and isotopically resemble low-grade rocks in the Michipicoten and Abitibi belts. In general, no major changes in whole-rock isotopic composition appear to have occurred during granulite facies metamorphism, implying limited flux of water or CO₂. The continuous linear gradient in ¹⁸O versus SiO₂ in the high-grade rocks cannot be due to differentiation of a mafic source magma. A model involving an association between mantle-derived mafic magma and ¹⁸O-enriched crustal materials is more consistent with the oxygen isotopic and the REE data.McMaster Isotopic, Nuclear and Geochemical Studies Group Publication 163; LITHOPROBE Publication 168.     

Sulfur and carbon isotope compositions in the stratiform Zn-Pb-Cu sulfide deposits of the Rajpura-Dariba belt,Rajasthan, NW India: A model of ore genesis

The sulfur isotope composition of 86 sulfide minerals from the Middle Proterozoic, metamorphosed, stratiform, sediment-hosted Zn-Pb-CU sulfide deposits of Dariba and Sindeswar Kalan located within the Rajpura-Dariba belt in Rajasthan, NW India, have been determined. In addition, 16 carbonaceous and 2 carbonate rock samples from the ore zone have been analyzed for their C_tot and C_org contents and carbon isotope compositions. The sulfur isotope compositions range from 9.1 to –6.7 (mean value of 1.9). Increasing ³⁴S values stratigraphically upward are observed, particularly for pyrite and pyrrhotite suggesting a syngenetic origin for the sulfur. No marked lateral isotopic variations or isotopic variation in minerals from successive laminae in banded ore samples occur. Fractionation of sulfur isotopes between coexisting sulfides suggests that the original isotopic pattern was basically preserved during the amphibolite-facies metamorphism suffered by the deposits. C_org in carbonaceous rocks ranges 0.5–9.3 wt%, with ¹³C values between –21 and –31 (mean of –25.4) in keeping with the biogenic derivation of the carbon. Recrystallized dolostones have ¹³C values close to –14.4Geological evidence and isotopic features are consistant with the following genetic scheme: (a) base-metal ores along the belt formed from geothermal emanations carrying H₂S, produced by the chemical reduction of seawater sulfates and leaching of mafic volcanics, in a semiclosed (with respect to SO₄), shallow-water, rift-related basin with high biological activity; (b) pyrite and pyrrhotite formed diagenetically by bacterial reduction of sulfate in pore seawater in a system open to H₂S, thus bringing about the gradual enrichment of ³⁴S in these minerals stratigraphically upward; and (c) northward in the belt, at Sindeswar Kalan, the basin of ore deposition was relatively more open.     

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.

     

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.     

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.

     

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.     

Sulphur isotope studies of the Mt Molloy,Dianne and O.K. stratiform sulphide deposits,Hodgkinson Province,North Queensland,Australia

Stratiform sulphide deposits which have been metamorphosed to lower greenschist facies occur within the Paleozoic strata of the Hodgkinson Province, northeast Queensland. Massive cupreous pyrite is ubiquitous and Mt Molloy and Dianne also have layered chalcopyrite-rich and sphalerite-rich lenses. Sulphide ³⁴S values for the mineralisation show a narrow spread, around 02030; at the Dianne and O.K. deposits, but a wider spread and an average several per mil higher at the Mt Molloy area. The minerals can not be used for geothermometry due to isotopic disequilibrium. However, metamorphic effects on the isotopic compositions appear not to have been significant. A decrease in temperature and contact of the ore fluid with sea water probably caused the precipitation of the ore minerals. A magmatic ore fluid with ³⁴S_S around 02030; predominated at the Dianne and OK deposits whereas the fluid at Mt Molloy mixed with sea water to acquire a higher ³⁴S_S value.     

Origins of metamorphic lode gold deposits: Implications of stable isotope data from the central Rocky Mountains,Canada

Summary The stable isotope geochemistry of native gold-bearing quartz veins contained within low-grade metasedimentary strata in the central Canadian Rocky Mountains, British Columbia is examined. The data augment previous geological and geochemical studies.Vein pyrite ³⁴S values cluster between + 14.2 and + 16.3 (CDT). Coeval galenas exhibit ³⁴S values between + 11.4 and 13.3. Pyrite-galena geothermometry reveals a mean temperature of mineralization of 300 ± 43°C. Comparison of ³⁴S values for the vein pyrites, with values for pyrite porphyroblasts in country rocks suggests that vein sulfur was probably derived from the host rocks.¹⁸O(SMOW) values of host quartzites and pelites cluster between + 12.0 and + 13.5, and + 9.5 and + 10.5, respectively. Auriferous vein quartz exhibits ¹⁸O values between + 13.0 and + 15.0. Veins were likely deposited from fluids undergoing post-peak metamorphic cooling.Vein inclusion fluids exhibit values between –105 and –124 (SMOW). Combined O-H-isotope data are most compatible with a source fluid involving chemically- and isotopically-evolved meteoric waters.The critical role of H-isotope data in the evaluation of source fluids for such mesothermal gold lodes is stressed. The paucity of H-isotope data pertaining to the study of lode gold deposits in similar low-grade metasedimentary domains suggests that the involvement of meteoric waters may at times be overlooked.

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Der Ursprung metamorphogener Gold-Ganglagerstätten: Bedeutung stabiler Isotopendaten aus den zentralen Rocky Mountains, Kanada

Zusammenfassung Die vorliegende Arbeit befaßt sich mit der Untersuchung der Geochemie stabiler Isotope goldführender Quarzgänge in schwach metamorphen Sedimenten der zentralen Rocky Mountains in Britisch Kolumbien, Kanada. Die Resultate ergänzen früher publizierte geologische und geochemische Daten.Die ³⁴S-Werte von Gang-Pyrit liegen zwischen + 14.2 und + 16.3 (CDT); gleichzeitig gebildeter Bleiglanz hat ³⁴S-Werte von + 11.4 bis + 13.3. Die Isotopengeothermo metrie des Pyrits und Bleiglanzes ergibt eine mittlere Mineralisationstemperatur von 300°C + 43° für diese beiden Minerale. Vergleiche der 8345-Werte des Gang-Pyrits mit denen von Pyrit-Porphyroblasten des Nebengesteins lassen für die Gang-Pyrite eine Herkunft des Schwefels aus dem Nebengestein als wahrscheinlich erscheinen.Die ¹⁸O-Werte von Quarziten und Peliten, die als Nebengesteine auftreten, streuen von + 12.0 bis + 13.5 (SMOW), beziehungweise von +9.5 bis + 10.5 Quarz goldführender Gänge hat ¹⁸O-Werte, die zwischen + 13.0 und + 15.0 (SMOW) liegen. Er wurde als Gangfüllung wahrscheinlich bei sinkenden Temperaturen aus post metamorphen wäßrigen Lösungen abgesetzt.Flüssigkeitseinschlüsse von Gangmineralien zeigen D-Werte von -105 bis -124 (SMOW). Die H-O-Isotope sind deshalb ein Hinweis dafür, daß als mineralisierende Lösungen isotopisch veränderte meteorische Wässer in Betracht zu ziehen sind. Bei der Deutung der Herkunft der mineralisierenden wäßrigen Lösungen von mesothermalen Goldgängen muß die Kenntnis der H-Isotope als kritisch betrachtet werden. Die Seltenheit mit der H-Isotopendaten dieses Lagerstättentyps in der Literatur diskutiert werden, dürfte ein wesentlicher Grund dafür sein, daß die Rolle meteorischer Wässer bei der Genese mesothermaler, in Metasedimenten liegender Goldgänge, vielfach übersehen wurde.

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With 4 Figures     

Isotopic Composition (δ13C, δ18O) and Origin of Manganese Carbonate Ores of the Usa Deposit (Kuznetskii Alatau)

Isotopic compositions of carbon and oxygen are studied in different (rhodochrosite, calcareous-rhodochrosite, and chlorite–rhodochrosite) types of manganese carbonate ores from the Usa deposit (Kuznetskii Alatau). The ¹³C value varies from –18.4 to –0.7, while the ¹⁸O value ranges between 18.4 and 23.0. Host rocks are characterized by higher values of ¹³C (–1.9 to 1.0) and ¹⁸O (21.2 to 24.3). The obtained isotope data suggest an active participation of oxidized organic carbon in the formation of manganese carbonates. Manganese carbonate ores of the deposit are probably related to metasomatic processes.     

The Rosita Hills epithermal Ag-Base metal deposits, Colorado, USA A stable isotope and fluid inclusion study

The Rosita Hills volcanic centre is an alkalicalcic, mid-Tertiary complex overlying orthoand paragneissic basement, on the eastern margin of the Rio Grande Rift in south central Colorado, USA. The centre contains vein-hosted, adularia-sericite type, epithermal Ag and base-metal mineralisation with minor Au. Stable isotope studies (O and H) of whole rock and mineral separate (quartz and sericite) samples from veins and hydrothermal eruption breccias show that the hydrothermal fluid had both magmatic and meteoric components. The D and ¹⁸O values of the hydrothermal fluid, calculated from mineral values, range from -22 to -103 and 0.5 to 5.9 respectively. Fluid inclusion data from vein minerals (quartz, baryte and sphalerite) and from an advanced argillic lithocap overlying the veins again show that the hydrothermal system had more than one component fluid. Fluid inclusions have salinities which range from 1.7 to 25.1 wt% NaCl equivalent and show evidence of boiling in the advanced argillic lithocap. Homogenisation temperatures range from 135°C to 298°C. Liquid CO₂ is present in some inclusions. These data indicate that a saline, isotopically heavy fluid mixed with a dilute, isotopically light fluid to precipitate the ore. We argue that the saline, isotopically heavy fluid is magmatic and derived from a resurgent rhyolitic magma below the mineralisation.     

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.     

Fluid regimes in the deformation of the Helvetic nappes,Switzerland, as inferred from stable isotope data

The stable isotope composition of veins, pressure shadows, mylonites and fault breccias in allochthonous Mesozoic carbonate cover units of the Helvetic zone show evidence for concurrent closed and open system of fluid advection at different scales in the tectonic development of the Swiss Alps. Marine carbonates are isotopically uniform, independent of metamorphic grade, where ¹³C=1.5±1.5 (1 ) and ¹⁸O=25.4±2.2 (1 ). Total variations of up to 2 in ¹³C and 1.5 in ¹⁸O occur over a cm scale. Calcite in pre- (Type I) and syntectonic (Type II) vein arrays and pressure shadows are mostly in close isotopic compliance with the matrix calcite, to within ±0.5, signifying isotopic buffering of pore fluids by host rocks during deformation, and closed system redistribution of carbonate over a cm to m scale. This is consistent with microstructural evidence for pressure solution — precipitation deformation.Type III post-tectonic veins occur throughout 5 km of structural section, extend several km to the basement, and accommodate up to 15% extension. Whereas the main population of Type III veins is isotopically undistinguishable from matrix carbonates, calcite in the largest of these veins is depleted in ¹⁸O by up to 23 but acquired comparable ¹³C values. This generation of veins involved geopressurized hydrothermal fluids at 200 to 350° C where ¹⁸O H₂O=–8 to +20, representing variable mixtures of ¹⁸O enriched pore and metamorphic fluids, with ¹⁸O depleted meteoric water. Calc-mylonites ( ¹⁸O=25 to 11) at the base of the Helvetic units, and syntectonic veins from the frontal Pennine thrust are characterized by a trend of ¹⁸O depletion relative to carbonate protoliths, due to exchange with an isotopically variable reservoir ( ¹⁸O H₂O=20 to 4). The upper limiting value corresponds to carbonate-buffered pore fluid, whereas the lower value is interpreted as ¹⁸O-depleted formation brines tectonically expelled at lithostatic pressure from the crystalline basement. Carbonate breccias in one of the large scale late normal faults exchanged with infiltrating ¹⁸O-depleted meteoric surface waters ( ¹⁸O=–8 to –10).During the main ductile Alpine deformation, individual lithological units and associated tectonic vein arrays behaved as closed systems, whereas mylonites along thrust faults acted as conduits for tectonically expelled lithostatically pressured reservoirs driven over tens of km. At the latest stages, marked by 5 to 15 km uplift and brittle deformation, low ¹⁸O meteoric surface waters penetrated to depths of several km under hydrostatic gradients.     

The sulfur and carbon isotope composition of scapolite-rich granulites from southern Tanzania

Sulfur and carbon isotope data are presented of 15 granulite samples from the Furua Complex, southern Tanzania, in which scapolite is a primary and major rock-forming constituent (up to 30 vol%). From these data, the isotopic composition is deduced of the sulfate and carbonate group in the scapolite structure. Subsequently, the composition and origin is discussed of the volatile species that are present in the deep crustal environment in which these scapolites formed.The ³⁴S-values show a narrow range from 0.3 to 3.6, consistent with a deep-seated (mantle) origin of the sulfur; the mean value of 1.9 is slightly higher than usually found in rocks of assumed mantle provenance. The results of the carbon isotope analyses are more difficult to interpret; they suggest that the granulites contain two different carbon components with different isotopic compositions. Firstly, one component, liberated by phosphoric acid at room temperature, has ¹³Cvalues between –3.8 and –11.2 and a mean value of –6.7. This carbon component is assumed to occur as finely dispersed, submicroscopic carbonate inclusions. The second carbon fraction is liberated by phosphoric acid treatment at temperatures between 200 and 400° C and has considerably lower ¹³Cvalues with a mean value of –14.1 This seems to represent the carbon isotope composition in the scapolite structure. Such low ¹³C-values do not agree with the generally accepted value of –7 for juvenile carbon, but they are comparable to those found in early, primary carbonic inclusions from various granulite regions. It is argued that these low ¹³C-values are typical for granulite-facies metamorphism and that they may characterize an important fluid phase of the lower crust.     

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 and phase equilibria of coesite-bearing whiteschists,Dora Maira Massif,western Alps

Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The ¹⁸O(smow) values of the quartz (after coesite) (¹⁸O=8.1 to 8.6, n=6), phengite (6.2 to 6.4, n=3), kyanite (6.1, n=2), garnet (5.5 to 5.8, n=9), ellenbergerite (6.3, n=1) and rutile (3.3 to 3.6, n=3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700–750 °C. Minimum pressures are 31–32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc+kyanite=pyrope+coesite+H₂O, the a(H₂O) must be reduced to 0.4–0.75 at 700–750 °C. The reduced a(H₂O) cannot be due to dilution by CO₂, as pyrope is not stable at X(CO₂)>0.02 (T=750 °C; P=30 kb). In the absence of a more exotic fluid diluent (e.g. CH₄ or N₂), a melt phase is required. Granite solidus temperatures are 680 °C/30 kb at a(H₂O)=1.0 and are calculated to be 70°C higher at a(H₂O)=0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H₂O) estimates for the whiteschist are 34±2 kb, 700–750 °C and 0.4–0.75. The oxygen isotope fractionation between quartz (¹⁸O=11.6) and garnet (¹⁸O=8.7) in the surrounding orthognesiss is identical to that in the coesitebearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (D(_SMOW)=-27 to-32), on secondary talc and chlorite rite after pyrope (D=-39 to -44) and on the surrounding biotite (D=-64) and phengite (D=-44) gneiss. All phases appear to be in nearequilibrium. The very high D values for the primary hydrous phases is consistent with an initial oceanicderived/connate fluid source. The fluid source for the retrograde talc+chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar D, but dissimilar ¹⁸O values of the coesite bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.     

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     

Geological,fluid inclusion and stable isotope studies of Mo mineralization,Galway Granite,Ireland

Mo mineralization within the Galway Granite at Mace Head and Murvey, Connemara, western Ireland, has many features of classic porphyry Mo deposits including a chemically evolved I-type granite host, associated K- and Si-rich alteration, quartz vein(Mace Head) and granite-hosted (Murvey) molybdenite, chalcopyrite, pyrite and magnetite mineralization and a gangue assemblage which includes quartz, muscovite and K-feldspar. Most fluid inclusions in quartz veins homogenize in the range 100–350°C and have a salinity of 1–13 eq. wt.% NaCl. They display Th-salinity covariation consistent with a hypothesis of dilution of magmatic water by influx of meteoric water. CO₂-bearing inclusions in an intensely mineralized vein at Mace Head provide an estimated minimum trapping temperature and pressure for the mineralizing fluid of 355°C and 1.2 kb and are interpreted to represent a H₂O-CO₂ fluid, weakly enriched in Mo, produced in a magma chamber by decompression-activated unmixing from a dense Mo-bearing NaCl-H₂O-CO₂ fluid. ³⁴S values of most sulphides range from c. 0 at Murvey to 3–4 at Mace Head and are consistent with a magmatic origin. Most quartz vein samples have ¹⁸O of 9–10.3 and were precipitated from a hydrothermal fluid with ¹⁸O of 4.6–6.7. Some have ¹⁸O of 6–7 and reflect introduction of meteoric water along vein margins. Quartz-muscovite oxygen isotope geothermometry combined with fluid inclusion data indicate precipitation of mineralized veins in the temperature range 360–450°C and between 1 and 2 kb. Whole rock granite samples display a clear ¹⁸O-D trend towards the composition of Connemara meteoric waters. The mineralization is interpreted as having been produced by highlyfractionated granite magma; meteoric water interaction postdates the main mineralizing event. The differences between the Mace Head and Murvey mineralizations reflect trapping of migrating mineralizing fluid in structural traps at Mace Head and precipitation of mineralization in the granite itself at Murvey.     

Contrasting fluid flow patterns at the Bufa del Diente contact metamorphic aureole,north-east Mexico: evidence from stable isotopes

Impure limestones with interstratified metachert layers were contact metamorphosed and metasomatized by the Bufa del Diente alkali syenite. Massive marbles exhibit mineralogical and stable isotope evidence for limited fluid infiltration, confined to a 17 m wide zone at the contact. Influx of magmatic brines along most metacherts produced up to 4 cm thick wollastonite rims, according to calcite (Cc)+quartz (Qz)= wollastonite (Wo)+CO₂, and were observed at distances of up to 400 m from the contact. The produced CO₂ exsolved as an immiscible low density CO₂-rich fluid. Chert protolith isotope compositions were ¹⁸O (Qz)=27–30%. and ¹⁸O (Cc)=24–27%.. Many wollastonites in infiltrated metacherts have low ¹⁸O ranging from 11–17 and confirm that decarbonation occurred in presence of a magmatic-signatured fluid. Large gradients in ¹⁸O (Wo) across the rims may reach 6 The ¹⁸O of remaining quartz is often lowered to 15–20 whereas caleites largely retained their original compositions. The isotopic reversals of up to 10 between quartz and calcite along with reaction textures demonstrate non-equilibrium between infiltrating fluid in the aquifer and the assemblage calcite+quartz+wollastonite. This is compatible with the assumption of a down-temperature flow of magmatic fluids that occurred exclusively in the remaining quarzite layer. The ¹³C (Cc) and ¹⁸O (Cc) of marble calcites measured perpendicular to two metachert bands reveal significant isotopic alterations along distances of 4.5 cm and 7.5 cm from the wollastonite-marble boundary only into the hanging wall marble, suggesting an advection process caused by a fluid phase which movel upwards. Covariation trends of ¹³C (Cc) and ¹⁸O (Cc) across the alteration front indicate that this fluid was CO₂-rich. Mass balance calculations show that all CO₂-rich fluid produced by the decarbonation reaction was lost into overlying marble. The metachert aquifers did not leak with respect to water-rich fluids.