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

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

Meteoric hydrothermal origin of calcites in “Green Tuff” formations,Miocene age,Japan

Oxygen and carbon isotope compositions were determined for calcites from the Green Tuff formations of Miocene age in Japan. Values of ¹⁸O from 24 calcites in altered rocks from 5 districts range from –2 to +16_SMOW, in most cases from 0 to +8_SMOW. The low ¹⁸O values rule out the possibility of their low-temperature origin or any significant contribution of magmatic fluid in the calcite precipitation. These values, coupled with their mineral assemblages, suggest that the calcites formed from meteoric hydrothermal solutions which caused propylitic alteration after the submarine strata became emergent.Values of ¹³C from the calcites show a wide variation from –17 to 0_PDB. Calcites from different districts have different ranges of ¹³C values, indicating that there was no homogeneous reservoir of carbon at the time the calcite formed, and that the carbon had local sources. Carbon isotopic compositions of calcite within ore deposits in the Green Tuff formations range from –19 to 0_PDB, similar to those of calcite in the altered rocks in the same district, suggesting that the carbon in ore calcites was likely supplied from the surrounding rocks through activity of meteoric hydrothermal solutions.     

Carbonization and geochemical characteristics of graphite-bearing rocks in the northern Khanka terrane,primorie, Russian Far East

Regional carbonization was examined in Riphean metamorphic complexes in the northern part of the Khanka terrane. The results obtained by various techniques of physicochemical analysis indicate that all petrographic rock varieties of this complex bear elevated concentrations (from 10⁻⁴ to 10⁻⁶ wt %) of Au and PGE. XRF data were used to describe a wide spectrum of trace elements: Ti, V, Ni, Cr, Pt, Pd, Re, Rh, Os, Ir, Cu, Hg, Au, Ag, Ta, Nb, Sr, Rb, Zr, La, W, Sn, Pb, and Zn. The Rb/Sr-Ba diagram shows the fields of anatectic granite-gneisses, biotite granites, lamprophyres, graphitized crystalline schists, black shales, skarns, and quartz-graphite metasomatic rocks. The C isotopic composition in graphite from the metaigneous rocks (lamprophyres and crystalline schists of the amphibolite facies) corresponds to δ¹³C from −8.5 to −8.7‰, which suggests that the carbon could be of endogenic provenance. The carbon isotopic composition of the greenschist-facies black shales corresponds to δ¹³C from −19.9 to −26.6‰, as is typical of organogenic carbon. The concentrations of precious metals in the rocks are, on average, one order of magnitude lower than in the graphitized crystalline schists. The origin of the precious-metal ore mineralization was likely genetically related to the regional carbonization process.     

Marine hdrothermal alteration at a Kuroko ore deposit,Kosaka, Japan

Isotopic compositions were determined for quartz, sericite and bulk rock samples surrounding the Uwamuki no. 4 Kuroko ore body, Kosaka, Japan. ¹⁸O values of quartz from Siliceous Ore (S.O.), main body of Black Ore B.O.) and the upper layer of B.O. are fairly uniform, +8.7 to +10.5. Formation temperatures calculated from fractionation of ¹⁸O between sericite and quartz from B.O. and upper S.O. are 250° to 300° C. The ore-forming fluids had ¹⁸O values of +1 and D values of –10, from isotope compositions of quartz and sericite.Tertiary volcanic rocks surrounding the ore deposits at Kosaka have uniform ¹⁸O values, +8.1±1.0 (n=50), although their bulk chemical compositions are widely varied because of different degrees of alteration. White Rhyolite, which is an intensely altered rhyolite occurring in close association with the Kuroko ore bodies, has also uniform ¹⁸O values, +7.9±0.9 (n=19). Temperatures of alteration are estimated to be around 300° C from the oxygen isotope fractionation between quartz and sericite. Paleozoic basement rocks phyllite and chert, have high ¹⁸O values, +18 and +19. The Sasahata formation of unknown age, which lies between Tertiary and Paleozoic formations, has highly variable ¹⁸O, +8 to +16 (n=4). High ¹⁸O values of the basement rocks and the sharp difference in ¹⁸O at their boundary suggest that the hydrothermal system causing Kuroko mineralization was mainly confined within permeable Tertiary rocks. D values of altered Tertiary volcanic rocks are highly variable ranging from –34 to –64% (n=12). The variation of D does not correlate with change of chemical composition, ¹⁸O values, nor distance from the ore deposits. The relatively high D values of the altered rocks indicate that the major constituent of the hydrothermal fluid was sea water. However, another fluid having lower D must have also participated. The fluid could be evolved sea water modified by interaction with rocks and the admixture of magmatic fluid. The variation in D may suggest that sea water mixed dispersively with the fluid.     

Stable isotope studies of the origins of mineralization at Mount Isa. I.

Further support for the view that mineralization at Mount Isa comprises two separate events is provided by ³⁴S/³²S measurement. Isotopic exchange between sulphides in lead-zinc-silver ores appears to have been promoted locally during metamorphism, whereas isotopic disequilibrium persists in the copper ores. These isotopic data are explained by a model in which sedimentary deposition of lead, zinc and silver was succeeded by the post-metamorphic emplacement of copper. Past biological activity is inferred from the occurrence of low concentrations of organic carbon with ¹³C values ranging from –21 to –26 PDB. Carbonate contents, expressed as carbon, vary from <0.1% to 10.9%. The ¹³C and ¹⁸O values for the carbonates are relatively constant at –4.4±1.1 and –17.6±1.1 PDB respectively. These values are interpreted as reflecting isotopic changes induced in original marine carbonates by isotopic exchange during lower greenschist metamorphism.     

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

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

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

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

Stable isotope and fluid inclusion studies of gem-bearing granitic pegmatite-aplite dikes,San Diego Co., California

Late Cretaceous, granitic pegmatite-aplite dikes in southern California have been known for gem-quality minerals and as a commercial source of lithium. Minerals, whole-rock samples, and inclusion fluids from nine of these dikes and from associated wall rocks have been analyzed for their oxygen, hydrogen, and carbon isotope compositions to ascertain the origins and thermal histories of the dikes. Oxygen isotope geothermometry used in combination with thermometric data from primary fluid inclusions enabled the determination of the pressure regime during crystallization.Two groups of dikes are evident from their oxygen isotope compositions (¹⁸O_qtz+10.5 in Group A, and +8.5 in Group B). Prior to the end of crystallization, Group A pegmatites had already extensively exchanged oxygen with their wall rocks, while Group B dikes may represent a closer approximation to the original isotopic composition of the pegmatite melts. Oxygen isotope fractionations between minerals are similar in all dikes and indicate that the pegmatites were emplaced at temperatures of about 730 ° to 700 ° C. Supersolidus crystallization began with the basal aplite zone and ended with formation of quench aplite in the pocket zone, nearly to 565 ° C. Subsolidus formation of gem-bearing pockets took place over a relatively narrow temperature range of about 40 ° C (approximately 565–525 ° C). Nearly closed-system crystallization is indicated.Hornblende in gabbroic and noritic wall rocks (D_w.r. = –90 to –130) in the Mesa Grande district crystallized in the presence of, or exchanged hydrogen with, meteoric water (D –90) prior to the emplacement of the pegmatite dikes. Magmatic water was subsequently added to the wall rocks adjacent to the pegmatites.Groups A and B pegmatites cannot be distinguished on the basis of their hydrogen isotope compositions. A decrease in D of muscovite inward from the walls of the dikes reflects a decrease in temperature. D values of H₂O from fluid inclusions are: –50 to –73 (aplite and pegmatite zones); –62 to –75 (pocket quartz: Tourmaline Queen and Stewart dikes); and –50 ± 4 (pocket quartz from many dikes). The average ¹³C of juvenile CO₂ in fluid inclusions in Group B pegmatites is –7.9. In Group A pegmatities, ¹³C of CO₂ is more negative (–10 to –15.6), due to exchange of C with wall rocks and/or loss of ¹³C-enriched CO₂ to an exsolving vapor phase.Pressures during crystallization of the pockets were on the order of 2,100 bars, and may have increased slightly during pocket growth. A depth of formation of at least 6.8 km (sp. gr. of over burden = 3.0, and P _fiuid=P _load) is indicated, and a rate of uplift of 0.07 cm/yr. follows from available geochronologic data.     

Sulphide-bearing Waters in Northern Apennines, Italy: General Features and Water-rock Interaction

Sulphide-bearing Ca-carbonate, Na-carbonate, Na-hydroxide, Na-chloride and Ca-sulphate waters from Northern Apennines were investigated in order to determine their main chemical and isotopic composition and draw inferences on water-rock interaction. ²H and ¹⁸O values suggest an origin mostly meteoric for the analysed waters but a well drilled in Miocenic sediments. The Na-carbonate and the Ca-sulphate waters are the most interesting geochemically. Na-carbonate type, which sometimes reaches extreme composition (Na/Ca up to 228, equivalent ratio), may have been derived through prolonged interaction of Ca-carbonate waters with rocks containing feldspar, montmorillonite and illite under calcite saturation/oversaturation; the high F and pH and the very low P_{CO 2} agree with prograde dissolution of silicates and lasting water-rock interaction. However, Ca–Na ion exchange, involving clays of marine origin, cannot be excluded in addition. The Ca-sulphate waters, occurring in Messinian gypsum-bearing sediments, are saturated in gypsum and calcite and exhibit very high total H₂S (up to 219 mg dm^-3) and P_{CO 2} (up to 0.32 bar). Mass balance of sulphate sulphur, sulphide sulphur and delta³⁴S suggests sulphate – derived from gypsum – as source for H₂S; CH₄ and organic matter generate the reducing conditions and sulphate reduction is mediated by bacteria. One Na-chloride water from a well in Miocenic sediments has unusual composition, containing about 700 mgdm^-3 of potential CaCl₂ and having ²H and ¹⁸O (-47.5 and -4.9 respectively) which plot far from the meteoric water lines; probably it is derived by mixing of meteoric and formation waters. The Na-hydroxide water, with very high pH (11.2), is generated through protracted interaction of meteoric waters with ultramafites.     

The platinum-group element distribution in the Dumont Sill,Quebec. Implications for the formation of ni-sulfide mineralization

Summary The Dumont Sill is an Archaean komatiitic intrusion, whichDuke (1986) subdivided into a mafic (MZ) and ultramafic zone (UMZ). The UMZ comprises an upper (UPZ) and a lower peridotite subzone (LPZ) consisting of olivine + chromite cumulates and a dunite subzone (DZ) between them, consisting of olivine ± sulfide cumulates.Three sulfide-rich layers in the DZ are delineated by anomalously high Ni, Cu, S and Se concentrations (Ni 0.95 wt %, Cu 0.07 wt.%, S 1.0 wt.%, Se 2.7 ppm). They also contain elevated contents of noble metals (Au 31.5 ppb, Pd 210 ppb, Pt 180 ppb, Ir 8.4 ppb, Os 6 ppb). Unmineralized samples contain 3–8 ppb Pd, 1–20 ppb Pt, 0.2–3.6 ppb Au, 0.5–6 ppb Ir, and 1–6 ppb Os.Samples belonging to the LPZ and UPZ and lying above and beneath the mineralized horizons have rather high Ir contents, generally between 2.9 to 4.4 ppb. In contrast, Ir contents of sulfide-free samples from the DZ and UPZ which lie immediately above the mineralized zones have significantly lower Ir concentrations, ranging from 0.1 to 1.5 ppb. This zone of Ir depletion coincides with a zone of Ni-depleted olivine and sulfide which crystallized just above sulfide-rich horizons in the DZ (Duke, 1986). It is suggested that Ir and Ni depletion in cumulates which lie between or above sulfide-rich zones are due to the lower Ir and Ni contents in olivine which crystallized from a silicate magma from which a sulfide liquid had already been segregated. Alternatively, if metal alloys control the distribution of Ir and Os in the DZ, the Ir depletion in the cumulates above the ore' horizons implies that crystallization of the metal phase ceased. This would be the case if, due to the segregation of sulfides, the Ir concentration in the silicate liquid falls below the solubility limit of the metal phase.The sulfide mineralization probably formed by fractional segregation of a sulfide/ oxide liquid, as the PGE concentrations in the sulfide liquid and PGE/Se, or PGE/S ratios tend to decrease from the bottom to the top in the mineralized zones.Duke (1986) proposed that sulfide saturation was caused by mixing of primitive komatiite magma with fractionated interstitial liquid, which was squeezed out of the cumulate pile. Sulfide segregation at the floor of the magma chamber is likely to have been a very localized event implying low R-factors. The small PGE-enrichment in the sulfide horizons of the Dumont Sill and the narrow zones of Ir-depletion just above the sulfide zones are consistent with the proposed process.

---

Die Verteilung von Platingruppen-Elementen im Dumont Sill, Quebec und ihre Bedeutung für die Bildung von Ni-Sulfid MIneralisationen

Zusammenfassung Der Dumont Sill ist eine komatiitische Intrusion, die von Duke (1986) in eine mafische (MZ) und eine ultramafische (UMZ) Zone untergliedert wurde. Die UMZ setzt sich aus einer oberen (UPZ) und einer unteren (LPZ) peridotitischen Subzone, die aus Olivinund Chromft-Kumulaten besteht, und einer dunitischen Subzone (DZ), zwischen diese beiden eingeschaltet, zusammen. Letztere besteht aus Olivin- und Sulfid-Kumulaten.Drei sulfidreiche Lagen innerhalb der DZ sind durch anomal hohe Gehalte an Ni, Cu, S und Se (Ni 0.95 Gew. %, Cu 0.07 Gew. %, S 1.0 Gew. %, Se 2.7 ppm) charakterisiert. Erhöhte Gehalte an Edelmetallen (Au 31.5 ppb, Pd 210 ppb, Pt 180 ppb, Ir 8.4 ppb, Os 6 ppb) sind ebenfalls an diese Lagen gebunden. Unvererzte Proben enthalten < 3–8 ppb Pd, 1–20 ppb Pt, 0.2–3.6 ppb Au, 0.5–6 ppb Ir und 1–6 ppb Os.Proben aus der LPZ und UPZ und solche aus dem Hangenden und Liegenden der Mineralisationshorizonte zeigen relativ hohe Ir-Gehalte; im allgemeinen zwischen 2.9 und 4.4 ppb. Im Gegensatz dazu sind die Ir-Gehalte sulfidfreier Proben unmittelbar über vererzten Lagen deutlich erniedrigt; sie variieren zwischen 0.1–1.5 ppb. Diese an Ir verarmte Zone entspricht einer Zone nickelarmer Olivine und Sulfide, die unmittelbar oberhalb der sulfidreichen Horizonte in der DZ kristallisierten (Duke, 1986). Es wird vermutet, daß die Ir- und Ni-Abreicherung in den Kumulaten, die oberhalb und zwischen den sulfid-reichen Zonen liegen, mit den niedrigeren Ir- und Ni-Gehalten der Olivinen zusammenhängt. Die Olivine kristallisierten aus einem Silikatmagma, von dem sich bereits eine Sulfidschmelze abgeschieden hatte.Soferne metallische Verbindungen die Ir- und Os-Verteilung in der DZ kontrollieren, würde die Ir-Abreicherung in den Kumulaten oberhalb des Erzhorizontes auf ein Ende der Kristallisation einer metallischen Phase hinweisen. Dieser Fall könnte eintreten, sobald durch die Ausscheidung von Sulfiden, die Ir-Konzentration in der silikatischen Schmelze unter die Löslichkeitsgrenze der Metallphase fällt.Die Sulfidvererzung bildete sich wahrscheinlich infolge von fraktionierter kristallisation einer Sulfid/Oxidschmelze, da die PGE Konzentrationen der Sulfidschmelze, und das PGE/S Verhältnis vom Liegenden zum Hangenden hin in den mineralisierten Horizonten abnehmen. Duke (1986) schlug ein Modell vor, in dem die Sulfid-Sättigung der silikatischen Schmelze durch eine Vermischung eines komatiitischen Magmas mit einer fraktionierten, interstitialen, aus den Kumulaten ausgequetschten Schmelze erklärt wird. Die Sulfidausfällung an der Basis der Magmenkammer scheint ein lokal recht begrenztes Phänomen gewesen zu sein, die niedrige R-Faktoren bedingt. Die geringfügige PGE-Anreicherung in den Sulfidlagen des Dumont Sills und die schmale Zone der Ir-Abreicherung unmittelbar oberhalb dieser sulfidischen Zone stehen mit diesen vorgeschlagenen Prozessen im Einklang.

---

---

With 6 Figures     

Changes in stable isotope ratios of metapelites and marbles during regional metamorphism,Mount Lofty Ranges,South Australia: implications for crustal scale fluid flow

The Mount Lofty Ranges comprises interlayered marbles, metapsammites, and metapelites that underwent regional metamorphism during the Delamarian Orogeny at 470–515 Ma. Peak metamorphic conditions increased from lowermost biotite grade (350–400°C) to migmatite grade (700°C) over 50–55 km parallel to the lithological strike of the rocks. With increasing metamorphic grade, ¹⁸O values of normal metapelites decrease from 14–16 to as low as 9.0, while ¹⁸O values of calcite in normal marbles decrease from 22–24 to as low as 13.2 These isotopic changes are far greater than can be accounted for by devolatilisation, implying widespread fluid-rock interaction. Contact metamorphism appears not to have affected the terrain, suggesting that fluid flow occurred during regional metamorphism. Down-temperature fluid flow from synmetamorphic granite plutons (¹⁸O=8.4–8.6) that occur at the highest metamorphic grades is unlikely to explain the resetting of oxygen isotopes because: (a) there is a paucity of skarns at granite-metasediment contacts; (b) the marbles generally do not contain low-XCO₂ mineral assemblages; (c) there is insufficient granite to provide the required volumes of water; (d) the marbles and metapelites retain a several permil difference in ¹⁸O values, even at high metamorphic grades. The oxygen isotope resetting may be accounted for by along-strike up-temperature fluid flow during regional metamorphism with time-integrated fluid fluxes of up to 5x10⁹ moles/m² (10⁵ m³/m²). If fluid flow occurred over 10⁵–10⁶ years, estimated intrinsic permeabilities are 10^-20 to 10^-16m². Variations in ¹⁸O at individual outcrops suggest that time-integrated fluid fluxes and intrinsic permeabilities may locally have varied by at least an order of magnitude. A general increase in XCO₂ values of marble assemblages with metamorphic grade is also consistent with the up-temperature fluid-flow model. Fluids in the metapelites may have been derived from these rocks by devolatilisation at low metamorphic grades; however, fluids in the marbles were probably derived in part from the surrounding siliceous rocks. The marble-metapelite boundaries preserve steep gradients in both ¹⁸O and XCO₂ values, suggesting that across-strike fluid fluxes were much lower than those parallel to strike. Up-temperature fluid flow may also have formed orthoamphibole rocks and caused melting of the metapelites at high grades.This paper is a contribution to IGCP Project 304 Lower Crustal Processes     

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

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

---

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

     

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     

Carbon and sulfur isotopic compositions of Early Cambrian black shales,NW Hunan,China: Implications for the Paleoceanographic sedimentary environment

In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.     

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.     

Possible non-equilibrium oxygen isotope effects in mantle nodules,an alternative to the Kyser-O'Neil-Carmichael18O/16O geothermometer

Kyser, O'Neil, and Carmichael (1981, 1982) measured the ¹⁸O values of coexisting minerals from peridotite nodules in alkali basalts and kimberlites, interpreting the nodules as equilibrium assemblages. Using Ca-Mg-Fe element-partition geothermometric data, they proposed an empirical¹⁸O/¹⁶O geothermometer: T(°C)=1,151–173–68 ², where is the per mil pyroxene-olivine fractionation. However, this geothermometer has an unusual crossover at 1,150 °C, and in contrast to what might be expected during closed-system equilibrium exchange, the most abundant mineral in the nodules (olivine) shows a much greater range in ¹⁸O (+4.4 to +7.5) than the much less abundant pyroxene (all 50 pyroxene analyses from spinel peridotites lie within the interval +5.3 to +6.5). On ¹⁸O-olivinevs. ¹⁸O-pyroxene diagrams, the mantle nodules exhibit data arrays that cut across the ¹⁸O=zero line. These arrays strongly resemble the non-equilibrium quartzfeldspar and feldspar-pyroxene ¹⁸O arrays that we now know are diagnostic of hydrothermally altered plutonic igneous rocks. Thus, we have re-interpreted the Kyser et al. data as non-equilibrium phenomena, casting doubt on their empirical geothermometer. The peridotite nodules appear to have been open systems that underwent metasomatic exchange with an external, oxygen-bearing fluid (CO₂, magma, H₂O, etc.); during this event, the relatively inert pyroxenes exchanged at a much slower rate than did the coexisting olivines and spinels, in agreement with available exchange-rate and diffusion measurements on these minerals. This accounts for the correlation between ¹⁸O pyroxene-olivine and the whole-rock ¹⁸O of the peridotites, which is a major difficulty with the equilibrium interpretation.Contribution No. 3978, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology     

Hydrogen and carbon isotope studies on the graphite-bearing metapelites in the northern Kiso district of central Japan

Measurements were made of the hydrogen isotope ratios of hydrous silicates (mica and amphibole) and whole rocks, and the carbon isotope ratios of graphite and carbonaceous matter in the metamorphic rocks from the northern Kiso district in central Japan.D values of hydrous silicates in the graphite-bearing metapelites are always higher than those in graphite-free schists, even though the sample localities of the two rock-types are very close. Hydrogen isotopic equilibrium has been attained between the coexisting minerals.D/H ratios of water in the metamorphic fluids seem to depend strongly on the presence or absence of graphite and seem to be not constant throughout the district. The district is divided into three areas of low (metamorphic zones I, II), medium (zones IIIa–V) and high ¹³C_gr value (zones VIa–VII) areas. In the high ¹³C_gr values area, the carbon contents of the graphite-bearing rocks decrease slightly from zones VIa to VII, whereas the ¹³C_gr values increase sharply from the upper part of zone VIa to VIb. TheD values of biotite in these graphite-bearing rocks are higher than those in the medium ¹³C_gr area. This suggests that methane enriched inH and¹²C is produced and liberated by the devolatilization reactions between muscovite, graphite and water. The fluid produced is composed of water, methane and a subordinate amount of carbon dioxide, and its logfO₂ value is deduced to be about 1.2 lower than that defined by the FMQ buffer. In the medium ¹³C_gr area, the ¹³C values of graphite are nearly constant (–20.8), while the Fe₂O₃/(Fe₂O₃ + FeO) ratio of the graphite-bearing rocks apparently decreases with increasing metamorphic grade.D differences in hydrous silicates between graphite-bearing and graphite-free rocks are observed. These facts are interpreted to mean that methane was produced in addition to water and carbon dioxide, and that its generation ( ratio of the fluid was about 2) had practically no isotope effect on the graphite. In the low ¹³C_gr area, the carbon contents of the rocks decrease clearly from zones I to IIIa. TheD and ¹³C_gr values of the non-metamorphosed shales are much lower than those of the low grade graphite-bearing metapelites. This suggests that methane is produced and liberated from the rocks even at the incipient stage of metamorphism.     

Carbon isotopic study on coexisting calcite and graphite in the Ryoke metamorphic rocks,northern Kiso district,central Japan

Carbon isotope fractionation between coexisting calcite and grpahite ( ¹³C_cc-gr) has been determined in metamorphosed limestones and calc-silicate rocks from the Ryoke metamorphic belt in the northern Kiso district. In this district, the Ryoke metamorphic rocks, ranging from the lower greenschist facies to the upper amphibolite facies, are widely distributed. The fractionation of ¹³C/¹²C between calcite and graphite decreases regularly with increasing metamorphic grade and is independent of absolute ¹³C values of calcite. This evidence suggests that carbon isotopic exchange equilibrium has been attained during metamorphism even in the greenschist facies and isotopic modification, possibly caused by retrogressive metamorphism, is not distinguished. For T=270–650° C, the fractionation is expressed by the following equation: ¹³C_cc-gr=8.9×10⁶T^–2–7.1 (T in °K).This equation has a slope steeper than the current results on the ¹³C_cc-gr versus 10⁶T^–2 diagram. It can be used as a potential geothermometer for almost the entire temperature range of metamorphism. ¹³C values of carbonaceous matter in unmetamorphosed limestones in this district are approximately –22, due to its biogenic origin. Graphite from metamorphosed limestones is also considered to be of biogenic origin but shows enrichment of ¹³C due to isotopic exchange with calcite. ¹³C values of graphite as well as ¹³C_cc-gr confirm that zone II represents the lowest grade zone of Ryoke metamorphism. The maximum equilibrium fractionation of ¹³C between calcite and graphite is considered to be approximately 23%, which corresponds to 270° C. Below this temperature, it seems that carbon isotopic exchange between the minerals does not occur.Calcite in marble from the higher grade zones has relatively lower ¹³C and ¹⁸O values. The depletion of heavy isotopes is considered to be caused by the loss of ¹³C and ¹⁸O enriched carbon dioxide during decarbonation reactions. For oxygen, it is considered that isotopic exchange with metamorphic fluids plays an important role in lowering the ¹⁸O value of calcite in some higher grade marbles.     

Multiphase evolution in the black-shale-hosted Ni–Cu–Zn–Co deposit at Talvivaara,Finland

The Talvivaara deposit contains 1550 Mt of ore averaging 0.22% Ni, 0.13% Cu, 0.49% Zn and 0.02% Co. The precursors of the host rocks were deposited 2.1–1.9 Ga ago in a stratified marine basin. Fractured talc-carbonate rocks delineate the eastern border of the deposit and serpentinites and talc-carbonate rocks occur along the rift-related sequence to the north and south of Talvivaara. Characteristic features are high concentrations of organic carbon and sulphur with median values of 7.6% and 8.2%, respectively. Organic carbon is graphitic at present and a variety of sulphide textures occur, representing multiphase evolution during diagenesis, tectonic deformation and medium-grade regional metamorphism. The main sulphides of the Talvivaara ore are pyrrhotite, pyrite, sphalerite, chalcopyrite and pentlandite. Sulphides occur both as fine-grained disseminations and coarse grains or aggregates. Chalcopyrite mainly occurs in joint surfaces and quartz-sulphide veins and pentlandite occur as inclusions in pyrrhotite. Alabandite (MnS) occurs in black shales and black metacarbonate rocks. The early low-T sulphide minerals were overprinted by later stage processes. No framboidal pyrite is any longer present, but spheroidal pyrite with a grain size of < 0.01 mm and containing up to 0.7% Ni occurs. During the deposition of the organic-rich mud the anoxic/euxinic bottom waters were enriched in Ni⁺, Cu⁺ and Zn^2 +. Sulphur isotope δ³⁴S values indicate mixing of sulphur derived from different processes or fractionation by sulphate reduction in a restricted basin. Both thermochemical and bacterial sulphate reductions were important for the generation of reduced sulphur.     

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.