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.     

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.     

Contrasting fluid/rock interaction between the Notch Peak granitic intrusion and argillites and limestones in western Utah: evidence from stable isotopes and phase assemblages

The Jurassic Notch Peak granitic stock, western Utah, discordantly intrudes Cambrian interbedded pure limestones and calcareous argillites. Contact metamorphosed argillite and limestone samples, collected along traverses away from the intrusion, were analyzed for ¹⁸O, ¹³C, and D. The ¹³C and ¹⁸O values for the limestones remain constant at about 0.5 (PDB) and 20 (SMOW), respectively, with increasing metamorphic grade. The whole rock ¹⁸O values of the argillites systematically decrease from 19 to as low as 8.1, and the ¹³C values of the carbonate fraction from 0.5 to –11.8. The change in ¹³C values can be explained by Rayleigh decarbonation during calcsilicate reactions, where calculated is about 4.5 permil for the high-grade samples and less for medium and low-grade samples suggesting a range in temperatures at which most decarbonation occurred. However, the amount of CO₂ released was not anough to decrease the whole rock ¹⁸O to the values observed in the argillites. The low ¹⁸O values close to the intrusion suggest interaction with magmatic water that had a ¹⁸O value of 8.5. The extreme lowering of ¹³C by fractional devolatilization and the lowering of ¹⁸O in argillites close to the intrusion indicates oxgen-equivalent fluid/rock ratios in excess of 1.0 and X(CO₂)_F of the fluid less than 0.2. Mineral assemblages in conjunction with the isotopic data indicate a strong influence of water infiltration on the reaction relations in the argillites and separate fluid and thermal fronts moving thru the argillites. The different stable isotope relations in limestones and argillites attest to the importance of decarbonation in the enhancement of permeability. The flow of fluids was confined to the argillite beds (argillite aquifers) whereas the limestones prevented vertical fluid flow and convective cooling of the stock.     

Modification of δD values in eastern Nevada granitoid rocks spatially related to thrust faults

Stable isotope data have been determined for 13 Mesozoic and Tertiary plutons in eastern Nevada and nearby Utah. In the southern Snake Range of eastern Nevada, where relations are best exposed and have been most intensively studied, D, ¹⁸O, and apparent K-Ar ages depend on proximity to the Snake Range decollement. Where stresses resulting from late movement on the decollement have caused cataclasis of Oligocene (37 Ma) granitoid rock, ¹⁸O, D, and K-Ar age values as low as –2.5, –155, and 18 Ma, respectively, have been determined. Where there has been no cataclasis, ¹⁸O values of Jurassic, Cretaceous, and Oligocene granitoid rocks are apparently unaffected, but both D values and K-Ar ages have been modified for distances of tens of meters below the decollement.Results similar to those in the southern Snake Range have been observed in other eastern Nevada granitoid rocks spatially related to regional thrust faults, as in the Kern Mountains, the Toana Range, and the northern Egan Range. In each of these areas cataclasis or deformation of granitoid rocks has resulted in lowered ¹⁸O, D, and K-Ar age values. Where there has been no cataclasis or deformation, ¹⁸O values are unaffected, but both D and K-Ar age values have been lowered by stresses resulting from postcrystallization movement along overlying thrust faults.Many of the plutons discussed have not been deeply eroded, and spatially related thrust faults crop out. Where thrust faults are not in evidence and the granitoid rocks give D values lower than about –130 along with spuriously low K-Ar age results, modification of the D and K-Ar age values may have been caused by stresses related to late movement along an overlying (now eroded) thrust fault.     

Contrasting serpentinization processes in the eastern Central Alps

Stable isotope compositions have been determined for serpentinites from between Davos (Arosa-Platta nappe, Switzerland) and the Valmalenco (Italy). D and ¹⁸O values (–120 to –60 and 6–10, respectively) in the Arosa-Platta nappe indicate that serpentinization took place on the continent at relatively low temperatures in the presence of limited amounts of metamorphic fluids that contained a component of meteoric water. One sample of chrysotile has a ¹⁸O value of 13 providing evidence of high W/R ratios and low formation temperature of lizardite-chrysotile in this area. In contrast, relatively high D values (–42 to –34) and low ¹⁸O values (4.4–7.4) for serpentine in the eastern part of the Valmalenco suggest a serpentinization process that took place at moderate temperatures in fluids that were dominated by ocean water. The antigorite in the Valmalenco is the first reported example of continental antigorite with an ocean water signature. An amphibole sample from a metasomatically overprinted contact zone to metasediments (D=-36) indicates that the metasomatic event also took place in the presence of ocean water. Lower D values (–93 to –60) of serpentines in the western part of the Valmalenco suggest a different alteration history possibly influenced by fluids associated with contact metamorphism. Low water/rock ratios during regional metamorphism (and metasomatism) have to be assumed for both regions.     

Upper miocene submarine basalts from the western margin of the Red Sea (Secca Fawn-l hole,massawa channel)

The Secca Fawn-1 hole, drilled in 1968 by Gulf Oil Co. on the western margin of Southern Red Sea, crossed at 1400 m depth a sequence of late Miocene-early Pliocene submarine basaltic flows, at least 600 m thick. This paper reports the results of the study of these basalts. Homogenous basaltic fragments were separated from 22 cuttings and analyzed for major elements; several trace elements were determined on 11 of these samples. All basalts have the composition of transitional olivine-tholeiites and a primary vertical variation, with a tendency towards a slightly more alkalic composition, was recognized in spite of the chemical changes induced by sea-water alteration which has affected rather deeply these rocks. Secca Fawn-1 basalts appear to be geochemically intermediate between typical low-K oceanic tholeiites as those erupted at Red Sea central trough and the transitional olivine-tholeiites of the spreading axes of the neighbouring Afar rift. K-Ar age results of 5.8 and 8.2 m. y. were obtained on two selected samples; these dates are however subject to caution because of the state of alteration of the samples. The structural implications of these data are discussed and it is thought that Secca Fawn-l basalts are related either to a localized spreading episode avorted in early Pliocene, or to extensional tectonics on the attenuated continental lithosphere of the Red Sea margin.

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Zusammenfassung Die Secca-Fawn-l-Bohrung, die 1968 von der Gulf Oil Company am westlichen Rand des südlichen Roten Meeres abgeteuft wurde, erreichte in 1400 m Tiefe eine Folge von jungmiozänen bis altpliozänen submarinen Basaltlagen, die mindestens 600 m mächtig sind. Es wurden homogene Basaltfragmente aus den Cuttings auf ihren Hauptelementgehalt hin analysiert; zahlreiche Spurenelemente wurden in einer Reihe dieser Proben bestimmt. Alle Basalte haben die Zusammensetzung von Übergangs-Olivin-Tholeiiten. Die primäre vertikale Veränderung zeigt eine zunehmende Tendenz zu mehr alkalischer Zusammensetzung, was auf eine chemische Veränderung durch Seewassereinfluß in diesen Gesteinen zurückgeführt werden kann. Die Secca-Fawn-1-Basalte erscheinen geochemisch zwischen typischen ozeanischen Tholeiiten mit niedrigen K-Werten, wie sie im Roten Meer im zentralen Graben auftreten, und Übergangs-Olivin-Tholeiiten entlang der spreading-Achse in der benachbarten Afar-Rift-Zone. Die K-Ar-Alter ergeben 5,8 und 8,2 m. y. Diese Alter sind jedoch mit Vorsicht zu betrachten, da die Proben einer sekundären Veränderung unterworfen waren. Als Folgerungen für die Strukturgeologie ergeben sich Zusammenhänge für eine frühe spreading-Episode im Altpliozän oder eine Dehnungstektonik in der kontinentalen Lithosphäre des Rotmeerrandes.

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Résumé Le sondage Secca Fawn-l, foré en 1968 par la Gulf Oil Co. sur le bord occidental de la Mer Rouge méridionale, a traversé, à la profondeur de 1400 mètres, une série épaisse de 600 mètres, faite de coulées basaltiques sous-marines d'âge Miocène supérieur à Pliocène inférieur. On en a analysé 22 fragments homogènes provenant de cuttings, et on en a déterminé les éléments majeurs ainsi que quelques éléments en traces dans 11 de ces échantillons. Tous les basaltes sont des tholéiites à olivine transitionnelles; une variation verticale primaire montrant dans les basaltes plus récents une tendance plus alcaline a été reconnue, ce qui peut être attribué à une altération chimique due à l'eau marine. — Du point de vue géochimique, les basaltes de Secca Fawn-1 sont intermédiaires entre des tholéiites océaniques pauvres en K, typiques, comme celles du Fossé central de la Mer Rouge, et les tholéiites à olivine transitionelles des axes d'expansion de la zone voisine du Rift de l'Afar.Des âges K-Ar de 5,8 et 8,2 m. a. ont été obtenus sur des échantillons provenant de la partie centrale de la série; mais ces datations doivent etre regardées avec précaution, car ces échantillons ont subi une altération secondaire. Les implications structurelles sont discutées; on envisage 2 possibilités: les basaltes de Secca Fawn-1 peuvent être liés soit à un épisode d'expansion localisée au début du Pliocène, ou bien à une tectonique disjonctive atténuée dans la lithosphère continentale du bord de la Mer Rouge.

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, 1968 Gulf Oil Company 1400 , 600 . ; . , . , . , / , , . - 5,8 8,2 , . , , , .

     

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 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 .     

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.     

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     

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.

     

A new discovery of possible primitive life-forms in conglomerates of the Archaean Pietersburg greenstone belt,South Africa

Spherical aggregates of carbonaceous matter measuring 0.2 to 1.0 mm in diameter were recently discovered in conglomerates of the Achaean Pietersburg greenstone belt in the Northern Transvaal, South Africa. Identical carbonaceous material, the so-called flyspeck carbon, occurs abundantly in the approximately 2'600 m. y. old sediments of the Witwatersrand Basin and has been considered to represent vegetative diaspores of primitive columnar plants. If this interpretation is correct, the occurrence of fly-speck carbon outside the Witwatersrand Basin indicates that differentiated life-forms also existed in other suitable depository environments and probably appeared earlier than previously thought.

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Zusammenfassung Im Nordtransvaal, Südafrika, wurde kürzlich kohlige Substanz in der Form rundlicher Aggregate entdeckt, die Durchmesser von 0,2 bis 1,0 mm besitzen und in Konglomeraten vorkommen, welche zum archaischen Pietersburg Greenstone Belt gehören. Ganz ähnlich ausgebildete kohlige Substanz, das sogenannte fly-speck carbon tritt in den rund 2600 Mio. Jahre alten goldführenden Konglomerathorizonten des Witwatersrand-Beckens verbreitet auf und wird dort als fossile Reste vegetativer Sporen von primitiven Pflanzen gedeutet. Trifft diese Interpretation der rundlichen Kohleaggregate zu, kann aus dem Auftreten von fly-speck carbon im Pietersburg Belt geschlossen werden, daß auch außerhalb des Witwatersrand-Beckens in geeigneten Ablagerungsräumen differenzierte Lebensformen existierten, möglicherweise schon vor der Ablagerung der Wirwatersrand-Sedimente, in denen solche Lebensformen bisher erstmals beschrieben wurden.

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Résumé Des agrégats spheriques de matière carbonée mesurant de 0.2 à 1.0 mm de diamètre ont été récemment découverts dans des conglomérats du Pietersburg Greenstone Belt d'âge archéen dans le Transvaal septentrional en Afrique du Sud. Du matériel carboné identique, connu comme »carbone en tâche de mouche« (fly-speck carbon), est abondant dans les sédiments datés de 2'600 m. a. du Bassin du Witwatersrand, et a été interprété comme les restes de spores végétatives de plantes columnaires primitives. Si cette interprétation est correcte, il s'en suit que la présence de »carbone en tâche de mouche« en dehors du Bassin du Witwatersrand indiquerait que des formes végétales différentiées existaient aussi dans d'autres environments de dépôts favorables et qu'elles ont apparu probablement plus tôt qu'on ne l'avait supposé jusqu'à présent.

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, , , 0,2 1 , , , , .. «fly-speck carbon», , 2600 , , . , «fly-speck carbon» , , , .

     

Schwefelisotope im marinen Kreislauf und das δ34 S der früheren Meere

Zusammenfassung Durch Isotopenfraktionierung bei der bakteriellen Reduktion marinen Sulfats enthalten die Sedimente im Mittel einen Überschuß an³²S (³⁴S s – 5), während³²S im marinen Sulfat angereichert ist. Der ³⁴S-Wert im heutigen Meerwasser beträgt etwa + 20 . Evaporit-³⁴S-Messungen zeigen, daß dieser Wert im Cambrium, Silur und Devon höher war, bis zum Perm dann auf etwa + 11 abnahm und anschließend wieder zum heutigen Wert anstieg.Der hohe ⁴³S-Wert in der geologischen Frühzeit wird mit extremer Anreicherung biogener Sulfide in den Schwarzschiefern erklärt, der Abfall zum Perm mit Rückführung großer Mengen von Sediment-Schwefel im Laufe der caledonischen und varistischen Orogenesen und der Wiederanstieg im Erdmittelalter mit erneuter Anhäufung toniger Sedimente.Aufgrund modellmäßiger Abschätzungen und der Gesamtheit aller verfügbaren Meßwerte (etwa 800) wird versucht, die Entwicklungslinie des Meerwasser-³⁴S-Wertes zeichnerisch darzustellen.Hinweis auf praktische Bedeutung: Informationen über Stoffbilanz geologischer Vorgänge, Interpretation von ³⁴S-Meßwerten an normalen Gesteinen und Erzen, Zuordnung von Proben unbekannten Alters.

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Summary Due to an isotope fractionation involved in the bacterial reduction of marine sulfate the sediments as a whole contain an excess of³²S (³⁴S – 5), while marine sulfate is enriched in³⁴S. Recent seawater has ³⁴S + 20. Evaporite measurements indicate a still higher value in Cambrian, Silurian and Devonian time. Then the ³⁴S decreased to about + 11 in the Upper Permian and later on increased once more to the modern value.The accumulation of abnormally large quantities of biogenic sulfides in the slates of that era accounts for the high ³⁴S value in the early Palaeozoic. A considerable fraction of light sulfur has been brought back to the oceans by weathering solutions of the Caledonian and Variscan orogenies, and in Mesozoic times another accumulation of slates has taken place.From a synopsis of the data available (some 800) and from model estimations an attempt has been made to construct the marine sulfur gd³⁴S evolution curve. Some practical consequences are lined out: informations on material balance of geological processes, interpretation of ³⁴S-data of normal rocks and ores, sample dating in the case of doubtful age.

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Résumé Un fractionnement isotopique pendant la réduction bactérienne du sulfate marin a pour conséquence un excédent de³²S dans la masse totale des sédiments (³⁴S – 5) et un enrichissement de³⁴S dans le sulfate marin. Dans les océans actuels le ³⁴S est + 20 ; nous pouvons conclure des ³⁴S des échantillons de sulfates d'évaporites, qu'aux temps cambrien, silurien et dévonien cette valeur fut plus élevée. Puis elle a diminué jusqu'à + 11 au Permien supérieur pour remonter ensuite à la valeur actuelle.La valeur élevée de ³⁴S au Paléozoïque inférieur doit être expliquée par une accumulation extraordinaire de sulfures biogènes dans les ardoises noires de cette époque. La décomposition d'une fraction considérable de ces roches pendant les orogenèses calédonienne et varisque entraînait à l'océan du soufre léger. Au Mésozoïque une autre accumulation d'ardoises commençait. Par l'examen de toutes valeurs disponibles (environ 800) et par certaines estimations on a tenté de tracer la courbe de l'évolution de la valeur du ³⁴S marin.Quelques conséquences pratiques sont indiquées: informations sur le bilan matériel des procès sus-géologiques, interprétation des ³⁴S de roches et minerais normaux, datation d'échantillons d'âge problématique.

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. S³⁴ , , ( 2%); 1,1%. .

     

Fluid-rock interaction between syenites and marbles at Stephen Cross Quarry,Québec,Canada: petrological and stable isotope data

Grenville dolomitic marbles and calc-silicates at Stephen Cross Quarry, Québec, underwent contact metamorphism and metasomatism associated with the intrusion of the Wakefield syenite at ambient pressures of 0.4GPa at 1090–1070Ma. Fluid infiltration produced exoskarns, calcite+periclase+forsterite±diopside±orthoclase assemblages in the marbles, and quartz±calcite±wollastonite±diopside±anorthite assemblages in the calc-silicates. Phase-equilibria in the CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ system suggest that fluid infiltration occurred close to the thermal peak of contact metamorphism (715–815°C) and that the fluids hadXCO₂0.15. In the metasediments, ¹⁸O values of calcite (Cc) are as low as 8.6, suggesting that the fluids were in isotopic equilibrium with the syenites (¹⁸O =8.8–10.2). Marble ¹³C(Cc) values are-0.1 to-3.2; the lack of correlation between ¹³C(Cc) and ¹⁸O(Cc) is consistent with the infiltration of water-rich fluids. The resetting of stable isotopes and the mineralogical changes can be explained by time-integrated fluid fluxes of up to 110 m³/m² (4×10⁶ mol/m²), corresponding to actual fluxes of 3×10^-11 to 3×10^-12 m³/m²-s and intrinsic permeabilities of 10^-18 to 10^-20 m² for fluid flow lasting 0.1-1Ma. Marble ¹⁸O(Cc) values do not correlate well with distance from the syenite, and fluids were probably channelled across lithological layering. The correlation between the degree of resetting of marble ¹⁸O(Cc) values with the abundance of submillimetre-wide veins, suggests that fluid focussing may have resulted from variations in fracture density. Late, lower temperature (<500°C), fluid flow formed serpentine (Serp) and brucite (Br) from periclase and forsterite. ¹⁸O(Br) and ¹⁸O(Scrp) values correlate with ¹⁸O(Cc), suggesting that retrogression involved only limited volumes of fluid. The observation that ¹⁸O(Cc-Br) and ¹⁸O(Cc-Serp) values are higher in marbles that have lower ¹⁸O(Cc) values is interpreted as indicating that fluid flow persisted to lower temperatures in those rocks due to higher intrinsic permeabilities. Calcite in the syenite was also formed by the influx of fluids during cooling. Syenite ¹⁸O(Cc) values are approximately in isotopic equilibrium with the high-temperature silicate minerals, suggesting that again only minor volumes of fluid were involved. In detail fluid flow was prolonged and complex, creating problems for the application of quantitative fluid flow models.This paper is a contribution to IGCP 304, Lower Crustal Processes     

Boninite petrogenesis and alteration history: constraints from stable isotope compositions of boninites from Cape Vogel,New Caledonia and Cyprus

¹⁸O values of unaltered olivine and pyroxene phenocrysts in boninites from several areas range from 5.8 to 7.4 and indicate that the source for most boninites is more ¹⁸O-rich than MORBs and other oceanic basalts. The source for oxygen and other major elements is most likely a refractory portion of the mantle having a ¹⁸O value of up to 7.0 to which must be added a small amount of H₂O-rich fluid to induce partial melting. This fluid, which is derived from subducted crust, is the vehicle for LREEs including Nd. The variable, normally low _Nd values typical of boninites do not correlate with the ¹⁸O values.Post eruptive exchange of oxygen in the glass of boninites with that of sea water at low temperatures (<150° C) produces ¹⁸O values of >10 in optically fresh glass. Hydration of the glass has increased the water contents of most boninites from estimated magmatic values of 1–2 wt% to 2–4 wt% and produced D values of < –80, which may be lower than the original magmatic D values. In contrast to most submarine pillow basalts, the magmatic volatile composition of boninite lavas has been extensively modified as a result of post eruptive interaction with seawater.     

O-Sr isotopic variations in Miocene granitoids from the Aegean: evidence for an origin by combined assimilation and fractional crystallization

Sr, O, and D/H isotopic compositions have been analyzed in Miocene metaluminous to slightly peraluminous (I-type) granitoids of the central Aegean. Individual plutonic complexes display significant variations in their ¹⁸O and initial⁸⁷Sr/⁸⁶Sr compositions.D and ¹⁸O compositions of minerals and whole-rocks are mostly in the magmatic range. Some samples from Naxos and Mykonos/Delos show low D and ¹⁸O values characteristic of meteoric-water-hydrothermal interaction, but as a whole the changes in ¹⁸O and Sr isotopic compositions as a result of hydrothermal alteration were slight, even in instances where marked alteration is petrographically observable. Consequently, the bulk-rock variations of ¹⁸O from 8.1 to 12.0 and of⁸⁷Sr/⁸⁶Sr from 0.70438 to 0.71450 may be regarded as primary and indicative of the conditions of their evolution. Heterogeneous isotopic compositions observed in the individual plutons of Serifos, Ikaria, Samos and Kos may be caused by the multiple intrusion of chemically and isotopically distinct magma pulses, with high viscosities and relatively rapid consolidation in most cases preventing complete homogenization. The granitoids of Serifos, Ikaria and Kos display weak correlations between the initial⁸⁷Sr/⁸⁶Sr and ¹⁸O and 1/Sr. The granitoid province shows a positive correlation between⁸⁷Sr/⁸⁶Sr and ¹⁸O and a non-linear relationship between⁸⁷Sr/⁸⁶Sr and 1/Sr, whereby 1/Sr increases more rapidly than the isotopic ratio as the degree of fractionation of the rocks increases. It is argued that assimilation of older continental material by mantle-derived arc magmas with combined fractionation (AFC) is the most plausible model to explain the chemical and isotopic characteristics of the granitoids and the geological situation in which rock-types trend from granodiorites in the (south)west, near the inferred Oligocene-Miocene suture, to granites in the center and monzonites in the (north)east of the province.     

Oxygen and hydrogen isotope compositions as indicators of granite genesis in the New England Batholith,Australia

Oxygen and hydrogen isotope studies of a number of granite suites and mineral separates from the New England Batholith indicate that O¹⁸ can be used to discriminate the major granite protoliths. The granite suites previously subdivided on the basis of mineralogical and geochemical criteria into S-type (sedimentary) and I-type (igneous) have O¹⁸ values consistently higher in the S-type granites (10.4–12.5) than in the spatially related I-type plutons (7.7–9.9). There appears to be a systematic variation in O¹⁸ from the most S-type to the most I-type granites, the dividing point between the two occuring at O¹⁸ equal to 10. A group of leucocratic granites that form about half of the batholith and difficult to classify mineralogically and geochemically is found to have low O¹⁸ values (6.4–8.1), suggesting an affinity to the most I-type granites. A single leucogranite pluton with minor muscovite has a O¹⁸ of 9.6 which is significantly higher than other leucogranites indicating a different origin perhaps involving amphibole fractionation.The behavior of D in the plutonic rocks is much less systematic than O¹⁸. Excluding samples collected adjacent to major faults, the D values show a rough positive correlation with water content similar to, but less pronounced than, the trend previously observed in the Berridale Batholith, southeastern Australia. This relation is considered to reflect an interaction between meteoric water and the granites, the largest effect being observed in samples with the least amount of water. Of note is the generally lower D values of the upper Paleozoic New England Batholith compared with the Silurian Berridale Batholith. This difference may be related to a near equatorial paleolatitude of 22 °S in the Silurian and near polar paleolatitudes in the late Carboniferous that have been inferred for these regions. Granite samples collected from near major faults, and one ignimbrite sample of rhyodacite composition, have very low D values (less than –120) suggesting a much greater degree of interaction with meteoric water.     

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.     

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.     

Hydrothermal alteration and oxygen and hydrogen isotope geochemistry of the D-68 zone Cu-Zn Massive Sulfide Deposit,Noranda District,Quebec, Canada

Summary Pervasive hydrothermal alteration zones in quartz-feldspar porphyry domes underly all massive sulfide lenses in the D-68 Zone Cu-Zn deposit, Noranda. Alteration pipes are mineralogically zoned and contain chloritic cores consisting of stringer sulfides, enveloped by sericitic haloes. Silicified rocks are found locally.Alteration took place at nearly constant volume. Na depletion, and K enrichment relative to the least altered rocks, are found in all alteration zones. Fe and Mg have been added to the chloritic zone and subtracted in the sericitic and silicic zones. Ca and Si are enriched mainly in the silicic zone. Al, Ti and Zr were the least mobile of the elements studied.Whole-rock ¹⁸O values vary from +5.6 to +6.2 per mil in chloritized rocks, +5.8 to + 7.3 per mil in sericitized rocks and + 7.2 to + 8.3 per mil in silicified rocks. D values for two chloritized samples are – 63 and – 70 per mil whereas in two sericitized samples they are close to –62 per mil. Quartz from the chlorite alteration zone is isotopically heavier (¹⁸O = 8.6 per mil) than that from the sericite alteration zone (¹⁸O = 6.4 per mil), suggesting equilibration with different hydrothermal fluid or different temperature of alteration. Assuming an alteration temperature of 300° + 50°C the fluid in equilibrium with quartz and chlorite had ¹⁸O and D values of about 1.5 ± 2.0 per mil and –23 ± 5 per mil, respectively. The fluid in equilibrium with quartz and sericite had ¹⁸O and D values of about –0.5 ± 2 per mil and –30 ± 5 per mil, respectively. On the basis of isotopic data, seawater was probably the major constituent of the hydrothermal fluids.

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Hydrothermale Umwandlung und Sauerstoff-Wasserstoff-Isotopengeochemie der Zone D-68 Cu-Zn Derberz Sulfidlagerstätte, Noranda District, Quebec, Canada

Zusammenfassung Hydrothermale Umwandlungszonen in porphyrischen Quarz-Feldspat Gesteinskörpern liegen unterhalb von Derberz Sulfidlinsen in der D-68 Zone Cu-Zn Lagerstätte, Noranda. Umgewandelte pipes sind mineralogisch zoniert; sie enthalten aus Sulfiden bestehende chloritische Kerne, die von sericitischen Höfen umhüllt werden. Lokal treten silicifizierte Gesteine auf.Die Umwandlung ging bei annähernd konstantem Volumen vor sich. Na-Verarmung und K-Anreicherung, bezogen auf die am wenigsten umgewandelten Gesteine, liegen in allen Umwandlungszonen vor. Fe und Mg wurden der Chloritzone zugeführt, in den Sericit- und Si-Zonen abgeführt. Ca und Si sind vor allem in der Si-Zone angereichert. Al, Ti und Zr waren von den untersuchten Elementen am wenigsten mobil.Gesamtgesteins-¹⁸O Werte variieren von +5,6 bis +6,2 in den chloritisierten Gesteinen, von +5,8 bis 7,3 in sericitisierten Gesteinen und von +7,2 bis +8,3 in den silicifizierten Gesteinen. Die D Werte für zwei chloritisierte Proben betragen –63 und –70, in zwei sericitisierten Proben liegen sie hingegen nahe bei –62. Quarz von der Chlorit-Umwandlungszone ist isotopisch schwerer (¹⁸O = 8,6) als von der Sericit-Umwandlungszone (¹⁸O = 6.4), was eine Gleichgewichtseinstellung mit verschiedenen hydrothermalen Lösungen oder eine verschiedene Umwandlungstemperatur nahelegt. Bei einer angenommenen Umwandlungstemperatur von 300 ± 50°C, hatte die im Gleichgewicht mit Quarz und Chlorit stehende Lösung ¹⁸O und D Werte von etwa 1,5 ± 2 bzw. –23 + 5. Die im Gleichgewicht mit Quarz und Sericit befindliche Lösung hatte ¹⁸O und D Werte von etwa –0,5 ± 2%o bzw. –30 ± 5. Aufgrund der Isotopendaten war wahrscheinlich Meerwasser der Hauptbestandteil der hydrothermalen Lösungen.

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With 7 Figures