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 .     

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.     

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 Candelaria silver deposit,Nevada — preliminary sulphur,oxygen and hydrogen isotope geochemistry

The pre-Cenozoic geology at Candelaria, Nevada comprises four main lithologic units: the basement consists of Ordovician cherts of the Palmetto complex; this is overlain unconformably by Permo-Triassic marine clastic sediments (Diablo and Candelaria Formations); these are structurally overlain by a serpentinitehosted tectonic mélange (Pickhandle/Golconda allochthon); all these units are cut by three Mesozoic felsic dike systems. Bulk-mineable silver-base metal ores occur as stratabound sheets of vein stockwork/disseminated sulphide mineralisation within structurally favourable zones along the base of the Pickhandle allochthon (i.e. Pickhandle thrust and overlying ultramafics/mafics) and within the fissile, calcareous and phosphatic black shales at the base of the Candelaria Formation (lower Candelaria shear). The most prominent felsic dike system — a suite of Early Jurassic granodiorite porphyries — exhibits close spatial, alteration and geochemical associations with the silver mineralisation. Disseminated pyrites from the bulk-mineable ores exhibit a ³⁴S range from — 0.3 to + 12.1 (mean ³⁴S = +6.4 ± 3.5, 1, n = 17) and two sphalerites have ³⁴S of + 5.9 and + 8.7 These data support a felsic magmatic source for sulphur in the ores, consistent with their proximal position in relation to the porphyries. However, a minor contribution of sulphur from diagenetic pyrite in the host Candelaria sediments (mean ³⁴S = — 14.0) cannot be ruled out. Sulphur in late, localised barite veins ( ³⁴S = + 17.3 and + 17.7) probably originated from a sedimentary/seawater source, in the form of bedded barite within the Palmetto basement ( ³⁴S = + 18.9). Quartz veins from the ores have mean ¹⁸O = + 15.9 ± 0.8 (1, n = 10), which is consistent, over the best estimate temperature range of the mineralisation (360°–460°C), with deposition from ¹⁸O-enriched magmatic-hydrothermal fluids (calculated ¹⁸O fluid = + 9.4 to + 13.9). Such enrichment probably occurred through isotopic exchange with the basement cherts during fluid ascent from a source pluton. Whole rock data for a propylitised porphyry ( ¹⁸O = + 14.2, D = — 65) support a magmatic fluid source. However, D results for fluid inclusions from several vein samples (mean = — 108 ± 14, 1, n = 6) and for other dike and sediment whole rocks (mean = — 110 ± 13, 1, n = 5) reveal the influence of meteoric waters. The timing of meteoric fluid incursion is unresolved, but possibilities include late-mineralisation groundwater flooding during cooling of the Early Jurassic progenitor porphyry system and/or meteoric fluid circulation driven by Late Cretaceous plutonism.     

Sulfur isotope ratios of Icelandic rocks

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

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

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

Isotopic Composition (δ13C, δ18O) of Carbonate Concretions from Terrigenous Deposits in the Northern Caucasus

The isotopic composition of carbon and oxygen was studied in carbonate concentrations with different compositions (calcite, dolomite, and siderite) from Jurassic, Cretaceous, and Tertiary terrigenous deposits of the Northern Caucasus. Wide variations in the isotopic composition (from 41.4 to 18.1 for ¹³C and from 11.7 to 33.5 for ¹⁸O) point to different formation conditions in the early diagenesis zone and the later catagenesis zone.     

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.     

Textural and isotopic variations in graphite from plutonic rocks,South-Central New Hampshire

Graphite occurs in two distinct textural varieties in syntectonic granitoids of the New Hampshire Plutonic Series and in associated metasedimentary wall rocks. Textural characteristics indicate that coarse graphite flakes were present at an early stage of crystallization of the igneous rocks and thus may represent xenocrystic material assimilated from the wall rocks. The range of ¹³C values determined for flake graphite in the igneous rocks (–26.5 to –13.8) overlaps the range for flake graphite in the wall rocks (–26.0 to –16.7), and spatial correlation of some ¹³C values in the plutons and wall rocks supports the assimilation mechanism. The textures of fine-grained irregular aggregates or spherulites of graphite, on the other hand, indicate that they formed along with secondary hydrous silicates and carbonates during retrograde reactions between the primary silicates and a carbon-bearing aqueous fluid phase. Relative to coexisting flake graphite, spherulitic graphite shows isotopic shifts ranging from 1.9 higher to 1.4 lower in both igneous and metasedimentary samples.The observed isotopic shifts and the association of spherulitic graphite with hydrous silicates are explained by dehydration of C-O-H fluids initially on or near the graphite saturation boundary. Hydration of silicates causes dehydration of the fluid and drives the fluid composition to the graphite saturation surface. Continued dehydration of the fluid then requires coprecipitation of secondary graphite and hydrous silicates and drives the fluid toward either higher or lower CO₂/CH₄ depending upon the inital bulk composition. Isotopic shifts in graphite formed at successive reaction stages are explained by fractionation of ¹³C between secondary graphite and the evolving fluid because ¹³C is preferentially concentrated into CO₂ relative to CH₄.Epigenetic graphite in two vein deposits assiciated with the contacts of these igneous rocks is generally enriched in ¹³C (–15.7 to –11.6) relative to both the igneous and wall-rock ¹³C values. Values of ¹³C vary by up to 3.4 within veins, with samples taken only 3 cm apart differing by 2.0 These variations in ¹³C correlate with textural evidence showing sequential deposition of different generations of graphite in the veins from fluids which differed in proportions of carbon species or isotopic composition (or both).     

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.     

Oxygen and carbon isotopic study on the genesis of the Steirischer Erzberg siderite deposit (Austria)

The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The ¹⁸O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in ¹⁸O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average ¹³C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower ¹³C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower ¹³C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average ¹³C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.     

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%. .

     

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     

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.     

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.     

Hydrothermal alteration and REE-Th mineralization at the Rodeo de Los Molles deposit,Las Chacras batholith,central Argentina

REE (rare-earth-element) and Th mineralization at the Rodeo de Los Molles deposit occurs within an elliptical body of hydrothermally altered rocks (fenite) located in a biotite monzogranite of the Las Chacras batholith. Ore assemblages are found as isolated patches of intergrown britholite, allanite, apatite, bastnaesite, fluorite, sphene, quartz, and aegirine-augite, as well as nodules of uranothorite and late-stage veins of calcite, fluorite, and bastnaesite. Composition-volume computations suggest that the fenite was produced by alteration of the biotite monzogranite by addition of K and Na, and loss of Ca and Sr. Petrographic evaluations indicate that microcline and plagioclase have been replaced by perthite, and biotite was converted to aggregates of clinochlore, anatase, kaolinite, and hematite. Relict biotite is characterized by lower Fe/(Fe+Mg) and Ti values with progressive alteration. Fluorine-rich phlogopite is present in mineralized areas, but textural evidence suggests that it was not produced via biotite alteration. Mass-balance constraints also show that Ca and Mg in ore zones may result from redistribution, rather than their being a result of external derivation. The ¹⁸O values of quartz (8.6–11.1) and feldspar (7.8–10.6) suggest that feldspar continued to exchange oxygen isotopes with a fluid to lower temperatures than did quartz. Feldspars equilibrated with a fluid of ¹⁸O8 at a fluid/rock ratio less than 1. The ¹⁸O values of quartz and aegirine-augite that crystallized during REE mineralization also suggest equilibration with a fluid of ¹⁸O8. The D values of biotite (-83 to-120) are relatively low for igneous rocks and are thought to have resulted from exsolution of a D-enriched magmatic vapor. The D values of both mineralized and barren fenites are consistent with equilibration with fluid of magmatic origin. Meteoric water was involved in the production of calcite and clinochlore alteration, and late-stage calcite-fluorite-bastnaesite veins. The ¹³C values of calcite and bastnaesite (-7.8 to-13.5%) suggest that carbon was derived by leaching of carbon from igneous and/or enclosing metamorphic rock types, and that a majority of carbon ultimately was derived from sedimentary organic meterial.     

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.     

Reconstruction of palaeohydrological conditions in a lagoon during the 2nd Zechstein cycle through simultaneous use of δD values of individual n-alkanes and δ<Superscript>18</Superscript>O and δ<Superscript>13</Superscript>C values of carbonates

For the first time ¹⁸O and ¹³C values from carbonates and D values of individual n-alkanes were used to reconstruct palaeohydrological conditions in a lagoon at the southern margin of the Central European Zechstein Basin (CEZB). A 12-m core covering the complete Ca2 interval and adjacent anhydrites (A1 and A2) was analyzed for ¹⁸O and ¹³C values of dolomitized carbonates and D values of individual n-alkanes. ¹⁸O_carb values (+2 to +5 vs. VPDB) were strongly influenced by evaporation and temporal freshwater input into the lagoon. The ¹³C_carb values (–1 to +4 vs. VPDB) were controlled mainly by changes in primary production. Both isotopic ratios show an inverse relationship throughout most of the core, contradicting diagenetic alteration, since ¹³C_carb values are not altered significantly during dolomitization. Assuming a temperature range of 35–40 °C in the lagoon, ¹⁸O_carb values of +2.5 to +8 (vs. VSMOW) for the lagoonal water can be reconstructed. The lagoon may have desiccated twice during the Ca2 interval, as indicated by very high ¹⁸O_carb and low ¹³C_carb values, coinciding with increasing amount of anhydrite in the analyzed sample. These events seem to reflect not just local but a regional intra-Ca2 cyclicity. Measured D values of the short-chain n-alkanes, namely n-C₁₆ and n-C₁₈ which are widely used as indicators for photosynthetic bacterial and algal input, reflect the isotopic composition of the lagoonal water. Assuming constant fractionation during incorporation of hydrogen into lipids of –160, an average D value of +70 (vs. VSMOW) can be reconstructed for the lagoonal water, accounting for very arid conditions. The long-chain n-alkanes n-C₂₇, n-C₂₈, n-C₂₉ and n-C₃₀, thought to be derived from the leaf waxes of terrestrial higher plants, were shown to be depleted in D relative to the short-chain alkanes, therefore indicating a different hydrogen source. Terrestrial plants in arid areas mainly use water supplied by precipitation. By using a smaller fractionation of –120 due to evaporation processes in the leaves, reconstructed values vary between –74 and –9 (vs. VSMOW). These values are not indicating extremely arid conditions, implying that the long-chain n-alkanes were transported trough wind and/or rivers into the lagoon at the Zechstein Sea coast. D_water values, reconstructed using the n-C₁₆ alkane and ¹⁸O _water values, independently reconstructed on the same sample using the temperature dependant fractionation for dolomites are good agreement and suggest high amounts of evaporation affecting the coastal lagoon. Altogether, our results indicate that hydrogen isotopic ratios of n-alkanes give information on their origin and are a useful proxy for palaeoclimatic reconstruction.     

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     

Preliminary investigations of 18O/16O and D/H compositions in rhyo-ignimbrites in the In Hihaou (In Zize) Magmatic Center,central Ahaggar,Algeria

The 620 M.y.-old in Hihaou (In Zize) magmatic complex located at the north-western boundary of the Archaean In Ouzzal block (western Ahaggar), is composed of massive alkaline rhyo-ignimbrites and rhyolitic domes, which are intruded by a granophyric and granitic body. The whole is preserved in a cauldron structure. Extrusive rocks are strongly ¹⁸O-depleted, with -values as low as –1.5/SMOW, while granophyres are less depleted (minimum -¹⁸O value=+2.0/SMOW. The granite has values around + 6/SMOW. D/H compositions are rather low, with D–90 to –110/SMOW. Isotopic zoning of quartz phenocrysts, ¹⁸O/¹⁶O fractionation among coexisting phases, and heterogeneity of the whole-rock -¹⁸O values, suggest that the volcanic rocks have interacted with meteoric water after the eruption. Several mechanisms of isotopic alteration are discussed. The hydrothermal alteration does not seem to have been controlled by the granitic intrusion, but rather seems to have followed the deposition of thick pyroclastic deposits on permeable arkosic sandstones and fluvio-glacial conglomerates. Pervasive circulation of water through the cooling volcanic deposits could have produced the observed ¹⁸O depletion.