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 oxygen isotopic composition of carbonates in lavas and ejectites from the Alban Hills,Italy

Carbon and oxygen isotopic analyses have been carried out on carbonates from lavas, ejectites and sedimentary formations in the region of the Alban Hills.The calcite occurring in the lavas, both in veins and cavities and dispersed in the groundmass shows within each flow a fairly uniform isotopic composition not different from that normally observed in sedimentary carbonates, except in the case of one particular flow, where unusually low ¹³C values were recorded. The latter are discussed in terms of a possible contribution of organic carbon or of isotopically light carbonates, the presence of which in the Alban Hills area had been previously recorded.The ejectites examined comprise both limestone and dolostone blocks of various degree of metamorphism and materials of uncertain origin, some of which containing carbon and oxygen of isotopic composition wholly different from that of all carbonates analysed in this work, approaching the range observed in some carbonatites. The isotopic data and the geochemical features of the latter materials are discussed in terms of thermal metamorphism of limestones and of a possible syntexis of evaporite materials.The ¹⁸O and ¹³C values of certain marine limestones from major Mesozoic sedimentary formations in the region are also reported.     

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

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

Oxygen and hydrogen isotope compositions of eclogites and associated rocks from the Eastern Sesia zone (Western Alps,Italy)

Oxygen and hydrogen isotope analyses have been made of mineral separates from eclogites, glaucophanites and glaucophane schists from the eastern Sesia zone (Italian Western Alps). Regularities in (1) hydrogen isotope compositions, (2) order of ¹⁸O enrichment among coexisting minerals, and (3) ¹⁸O (quartz-rutile) and ¹⁸O (quartz-phengite) imply attainment of a high degree of isotopic equilibrium. However, some scattering of ¹⁸O values of individual minerals indicates that the eclogitic assemblage did not form in the presence of a thoroughly pervasive fluid. Minerals from an eclogitic lens enclosed in marble have ¹⁸O values distinctly different from those measured in the other rocks. The ¹⁸O values are high in comparison with other type C eclogites of the world, and it is proposed that the fluid present during the high pressure metamorphism has to a large extent been inherited from the precursor rocks of amphibolite facies.An average formation temperature of 540 ° C is inferred from the oxygen isotope fractionations between quartz and rutile and between quartz and white mica. This temperature is in accordance with petrologic considerations and implies subduction of the precursor rocks into the upper mantle to achieve the high pressures required.     

Schwefelisotopenuntersuchungen an einigen Sulfid- und Sulfatmineralen der Blei-Zink-Erzlagerstätte Bleiberg/Kreuth,Kärnten

Zusmmenfassung Die Ergebnisse der Schwefelisotopenanalysen von sechs Sulfid- und vier Sulfatmineralproben von Bleiberg/Kreuth (Österreich) variieren von –6,9 bis –25,9 ³⁴S in den Sulfiden und von +14,8 bis +18,9 ³⁴S in den Sulfaten. Die große Variationsbreite der Schwefelisotopen und die Bevorzugung des leichten Schwefels deutet vermutlich auf bakterielle Prozesse der Sulfidfällung. Die Sulfatschwefel fallen in den Bereich der Schwefelisotopenzusammensetzung des mesozoischen (postskytischen) Meerwassers.

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Determination of the sulfur isotopic composition in some sulfide and sulfate minerals of the lead zinc deposit, Bleiberg/Kreuth, Carinthia

Summary Results of sulfur isotope analyses on 6 sulfides and 4 sulfates from Bleiberg/Kreuth (Austria) range from –6.9 to –25.9 ³⁴S (in sulfides) and from +14.8 to +18.9 ³⁴S (in sulfates). A large range of sulfide sulfur isotope fractionation with appreciable light sulfur probably indicates a bacterial sulfur source in sulfide precipiation. The sulfate sulfur plots in the range of Mesozoic (post-Skytian) seawater sulfur isotopic composition.

     

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

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

Oxygen-isotope geochemistry of metamorphosed,massive sulfide deposits of the Flin Flon — Snow Lake belt,Manitoba

Oxygen-isotope compositions have been measured for whole-rock and mineral samples of host and hydrothermally altered rocks from three massive sulfide deposits, Centennial (CL), Spruce Point (SP), and Anderson Lake (AL), in the Flin Flon — Snow Lake belt, Manitoba. Wholerock ¹⁸O values of felsic metavolcanic, host rocks (+8.5 to +16.1) are higher than those of altered rocks from the three deposits. The ¹⁸O values of altered rocks are lower in the chlorite zone and muscovite zone-I (CL=+ 5.3; SP=+5.4 to +8.3; AL= +3.7 to +5.9) than in the gradational zone (CL= +9.9 to +11.7; SP= +8.4 to +9.8; AL= + 6.6 to +7.7). Muscovite schist (Muscovite Zone-II) enveloping the Anderson Lake ore body has ¹⁸O values of +7.2 to +8.3. Quartz, biotite, muscovite, and chlorite separated from the altered rocks have lower ¹⁸O values compared to the same minerals separated from the host rocks. However, isotopic fractionation between mineral-pairs is generally similar in both host and altered rocks.It is interpreted that differences in the oxygen-isotope compositions of the altered and host rocks were produced prior to metamorphism, during hydrothermal alteration related to ore-deposition. Isotopic homogenization during metamorphism occurred on a grain-to-grain scale, over no more than a few meters. The whole-rock ¹⁸O values did not change significantly during metamorphism. The generally lower ¹⁸O values of altered rocks, the Cu-rich nature of the ore and the occurrence of the muscovite zone-II at Anderson Lake are consistent with the presence of higher temperature hydrothermal fluids at Anderson Lake than at the Centennial and Spruce Point deposits.     

Equilibrium relations of prograde metamorphic mineral assemblages

¹⁸O of quartz, biotite, muscovite, garnet, ilmenite or magnetite, K-feldspar, and D of biotite from prograde metamorphic pelites of the Damara Orogen have been analyzed. The samples were taken from one stratigraphic unit which is exposed in the various stages from low-grade up to high-grade metamorphism with anatexis. Using the fractionation curves experimentally investigated up to now, it can be shown that equilibrium has been reached among the metamorphic assemblages in the low-grade and lower medium-grade metamorphism only. In the high-grade rocks only a partial equilibrium exists between those phases formed at the specific high-grade isogrades, i.e., K-feldspar, garnet, magnetite, or ilmenite, but not between these and the main reacting phase biotite. Biotite in equilibrium with these minerals is foundonly in anatectic rocks where new biotite crystallized from the melt.From this it is concluded that the¹⁸O/¹⁶O ratio of biotite is fixed at the time of crystallization and its initial composition is preserved when the temperature increases, unless the biotite recrystallizes. The isotopic temperatures derived from mineral pairs formed at specific isograds are in excellent agreement with temperatures derived from petrological investigations. The hydrogen isotoperatio of biotites decreases with increasing grade of metamorphism.     

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     

Fluid heterogeneity during granulite facies metamorphism in the Adirondacks: stable isotope evidence

The preservation of premetamorphic, whole-rock oxygen isotope ratios in Adirondack metasediments shows that neither these rocks nor adjacent anorthosites and gneisses have been penetrated by large amounts of externally derived, hot CO₂-H₂O fluids during granulite facies metamorphism. This conclusion is supported by calculations of the effect of fluid volatilization and exchange and is also independently supported by petrologic and phase equilibria considerations. The data suggest that these rocks were not an open system during metamorphism; that fluid/rock ratios were in many instances between 0.0 and 0.1; that externally derived fluids, as well as fluids derived by metamorphic volatilization, rose along localized channels and were not pervasive; and thus that no single generalization can be applied to metamorphic fluid conditions in the Adirondacks.Analyses of 3 to 4 coexisting minerals from Adirondack marbles show that isotopic equilibrium was attained at the peak of granulite and upper amphibolite facies metamorphism. Thus the isotopic compositions of metamorphic fluids can be inferred from analyses of carbonates and fluid budgets can be constructed.Carbonates from the granulite facies are on average, isotopically similar to those from lower grade or unmetamorphosed limestones of the same age showing that no large isotopic shifts accompanied high grade metamorphism. Equilibrium calculations indicate that small decreases in ¹⁸O, averaging 1 permil, result from volatilization reactions for Adirondack rock compositions. Additional small differences between amphibolite and granulite facies marbles are due to systematic lithologie differences.The range of Adirondack carbonate ¹⁸O values (12.3 to 27.2) can be explained by the highly variable isotopic compositions of unmetamorphosed limestones in conjunction with minor ¹⁸O and ¹³C depletions caused by metamorphic volatilization suggesting that many (and possibly most) marbles have closely preserved their premetamorphic isotopic compositions. Such preservation is particularly evident in instances of high ¹⁸O calcites (25.0 to 27.2), low ¹⁸O wollastonites (–1.3 to 3.5), and sharp gradients in ¹⁸O (18 permil/15m between marble and anorthosite, 8 permil/25 m in metasediments, and 6 permil/1 m in skarn).Isotopic exchange is seen across marble-anorthosite and marble-granite contacts only at the scale of a few meters. Small (<5 m) marble xenoliths are in approximate exchange equilibrium with their hosts, but for larger xenoliths and layers of marble there is no evidence of exchange at distances greater than 10 m from meta-igneous contacts.     

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 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.     

An oxygen isotope study of the Loon Lake pluton and the Apsley gneiss,Ontario

The Loon Lake pluton in the Grenville province of Southeastern Ontario consists of a quartz monzonite rim surrounding a monzonite core containing inclusions of gneiss, gabbro and diorite. The pluton was emplaced in amphibolite facies Apsley gneiss, amphibolite and marble. Abnormally high ¹⁸O values are observed in all igneous rock types: quartz monzonite (8.9–13.9), monzonite (8.9–9.7), diorite-gabbro (8.0–9.3). High ¹⁸O contents are attributable to interaction between pluton and country rocks, through either isotopic exchange or direct mixing of mobilizate anatectically produced in the contact aureole of the pluton.The Apsley gneiss displays a ¹⁸O range from 8.3 to 16.9. There is no difference in ¹⁸O distribution between rocks inside and outside the contact aureole, although intermineral isotopic fractionations in the aureole are smaller than those outside. A chemical composition discriminant function that distinguishes rocks of igneous origin (DF>0) from sedimentary (DF<0) is inversely correlated with ¹⁸O of the gneisses, indicating that low ¹⁸O values are inherited from a silicic volcanic protolith. Al₂O₃/Na₂O, an index of maturity of sediments, increases with ¹⁸O for the DF<0 group but is almost constant for the DF>0 group over a ¹⁸O range from 8.3 to 13.4. The DF<0 group is inferred to have formed from a series of clastic sediments of varying degree of weathering or maturity; the DF>0 group formed either from tuffs partially altered to zeolites, or from hydrated volcanic flows or ignimbrites.     

Stable isotopic evidence for large-scale seawater infiltration in a regional metamorphic terrane; the Trois Seigneurs Massif,Pyrenees, France

Oxygen isotopic analyses of 95 metamorphic and igneous rocks and minerals from a Hercynian metamorphic sequence in the Trois Seigneurs Massif, Pyrenees, France, indicate that all lithologies at higher metamorphic grades than the andalusite in isograd have relatively homogeneous ¹⁸O values. The extent of homogenization is shown by the similarity of ¹⁸O values in metacarbonates, metapelites and granitic rocks (+11 to +13), and by the narrow range of oxygen isotopic composition shown by quartz from these lithologies. These values contrast with the ¹⁸O values of metapelites of lower metamorphic grade ( ¹⁸O about +15). Homogenization was caused by a pervasive influx of hydrous fluid. Mass-balance calculations imply that the fluid influx was so large that its source was probably high-level groundwaters or connate formation water. Hydrogen isotopic analyses of muscovite from various lithologies are uniform and exceptionally heavy at D=–25 to –30, suggesting a seawater origin. Many lines of petrological evidence from the area independently suggest that metamorphism and anatexis of pelitic metasediment occurred at depths of 6–12 km in the presence of this water-rich fluid, the composition of which was externally buffered. Deep penetration of surface waters in such environments has been hitherto unrecognized, and may be a key factor in promoting major anatexis of the continental crust at shallow depth. Three types of granitoid are exposed in the area. The leucogranites and the biotite granite-quartz diorite are both mainly derived from fusion of local Paleozoic pelitic metasediment, because all these rocks have similar whole-rock ¹⁸O values (+11 to +13). The post-metamorphic biotite granodiorite has a distinctly different ¹⁸O (+9.5 to +10.0) and was probably derived from a deeper level in the crust. Rare mafic xenoliths within the deeper parts of the biotite granite-quartz diorite also have different ¹⁸O (+8.0 to +8.5) and possibly represent input of mantle derived magma, which may have provided a heat source for the metamorphism.Contribution No. 4192, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology     

Stable and Sr-isotope evidence for fluid advection during thrusting of the glarus nappe (swiss alps)

At the Glarus thrust in the Swiss Helvetic Alps, Permian Verrucano siltstones are allochthonously superimposed over Tertiary Flysch with an intermediate, about 1 metre thin layer of intensively deformed calcmylonite of probable Mesozoic provenance. The H–O–C- and Sr-isotope compositions of minerals from the calc-mylonite and strongly mylonitized Verrucano siltstones were determined in order to assess: (1) equilibrium-disequilibrium relationships; (2) isotopic composition of the fluid phase, its provenance and water/rock ratios; (3) sources of Sr in the calc-mylonite; (4) deformation temperatures. The isotopic composition of cale-mylonite micro-samples from five sites along the thrust varies from 22 to 12 and 2 to-10 for ¹⁸O and ¹³C respectively. All samples are ¹⁸O depleted by up to 14 relative to the presumed marine Helvetic carbonate protoliths (¹⁸O=25.4±2). A pronounced geographic trend of ¹⁸O depletion from 22 in the north to 12 in the south is observed. In calc-mylonites, ⁸⁷Sr/⁸⁶Sr ratios range from typical Mesozoic marine carbonate protolith signatures (0.708±0.005) to more radiogenic values as high as 0.722. A variable contribution of radiogenic ⁸⁷Sr to the calc-mylonite is though to reflect interaction with fluids that aquired their Sr from the Hercynian granitic basement. Chlorites and muscovites from the calc-mylonite and Verrucano have uniform ¹⁸O values but display D values from-40 to-147%: the D-enriched values correspond to the primary metamorphic or formational fluids expelled during thrusting, whereas the D-depleted samples reflect selective H-isotope exchange with meteoric fluids during uplift of the Alpine belt. The isotopic composition of the calc-mylonites requires exchange with ¹⁸O—depleted, ⁸⁷Sr—enriched fluids at very high water/rock ratios. Possible sources for these are dewatering of the underlying Flysch and/or metamorphic fluids, or formation brines expelled along the thrust from greater depth. These could be derived from compaction and dewatering of the Flysch in the northern part of the thrust; in the south, however, where Verrucano is thrust over ¹⁸O-rich Mesozoic carbonates, the extreme ¹⁸O depletion of the calc-mylonite has to be explained either by fluid advection within the Verrucano hanging wall and thrust zone or alternatively by exchange with metamorphic fluids from greater depth, expelled along the thrust. Microstructural evidence (abundant veins, stylolites, breccias) suggests that fluids played an important role in deformation and strain localization. Excepting albite all major components (quartz, chlorite, muscovite, calcite) are both dynamically recrystallized and crystallized as secondary minerals in pressure shadows and syn-mylonitic veins, indicating that these minerals were potentially open to oxygen isotopic exchange during alpine metamorphism and thrust deformation. Within the mylonitized Verrucano silstones, isolated quartz-chlorite and quartz-calcite fractionations yield temperatures of around 320°C close to values obtained from calcite-dolomite thermometry (355°C±30) and in agreement with the regional lower greenschist facies metamorphism. Quartz-calcite and quartz-albite fractionations indicate slightly lower temperatures around 250°C, owing to selective lower temperature re-equilibration of the calcite and albite during post peak metamorphism.     

Oxygen and hydrogen isotope evidence for meteoric water infiltration during mylonitization and uplift in the Ruby Mountains-East Humboldt Range core complex,Nevada

Stable isotope analyses of rocks and minerals associated with the detachment fault and underlying mylonite zone exposed at Secret Creek gorge and other localities in the Ruby-East Humboldt Range metamorphic core complex in northeastern Nevada provide convincing evidence for meteoric water infiltration during mylonitization. Whole-rock ¹⁸O values of the lower plate quartzite mylonites (95% modal quartz) have been lowered by up to 10 per mil compared with structurally lower, compositionally similar, unmylonitized material. Biotite from these rocks has D values ranging from -125 to -175, compared to values of -55 to-70 in biotite from unmylonitized rocks. Mylonitized leucogranites have large disequilibrium oxygen isotope fractionations ( ^{quartz-feldspar} up to 8 per mil) relative to magmatic values ( ^{quartz-feldspar}1 to 2 per mil)). Meteoric water is the only major oxygen and hydrogen reservoir with an isotopic composition capable of generating the observed values. Fluid inclusion water from unstrained quartz in silicified breccia has a D value of-119 which provides a plausible estimate of the D of the infiltrating fluid, and is similar to the isotopic composition of present-day and Tertiary local meteoric water. The quartzite mylonite biotites would have been in equilibrium with such a fluid at temperatures of 480–620° C, similar to independent estimates of the temperature of mylonitization. The relatively high temperatures required for isotopic exchange between quartz and water, the occurrence of fluid inclusion trails and deformed veins in quartzite mylonites, and the spatial association of the low-¹⁸O, low-D rocks with the shear zone all constrain isotopic exchange to the mylonitic (plastic) deformation event. These observations suggest thata significant amount of meteoric water infiltrated the shear zone during mylonitization to depths of at least 5 to 10 km below the surface. The depth of penetration of meteoric fluids into the lower plate mylonites was at least 70 meters below the detachment fault. In contrast, the upper-plate unmylonitized fault slices are dominated by brittle fracture and are often intensely veined (carbonates) or silicified (volcanic rocks and breccias). The fluids associated with the veining and silicification were also meteoric as evidenced by low ¹⁸O values of the veins, which are often 10 per mil lower than the adjacent carbonate matrix, and the exceptionally low ¹⁸O values (down to-4.4) of the breccias. Several previous studies have documented the infiltration of meteoric fluids into the brittley deformed upper plate rocks of core complexes, but this study provides convincing evidence that surface fluids have penetrated lower plate rocks undergoing plastic deformation. It is proposed that infiltration took place as the shear zone began the transition from plastic flow to brittle fracture while the lower plate rocks were being uplifted. During this period, plastic flow and brittle fracture were operating simultaneously, perhaps allowing upper plate meteoric fluids to be seismically pumped down into the lower plate mylonites.     

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.     

Oxygen isotope heterogeneity of the mantle deduced from global 18O systematics of basalts from different geotectonic settings

Based upon a compilation and analysis of O-isotope data for Neogene volcanic rocks worldwide, the ¹⁸O variation for 743 basalts (historic lavas, submarine glasses, and lavas with <0.75 wt% H₂O) is +2.9 to +11.4. Mid-ocean-ridge basalt (MORB) has a uniform O-isotope composition with ¹⁸0=+5.7±0.2. Basalts erupted in different tectonic settings have mean ¹⁸O/¹⁶O ratios that are both lower and higher than MORB, with continental basalts enriched in ¹⁸O by ca. 1 over oceanic basalts. The ¹⁸O range for the subset of 88 basalts with Mg# [100·Mg(Mg+Fe²⁺)] 75–68, considered to be unmodified primary mantle partial melts, is +3.6 to +8.7. These features are a clear indication that: (1) the Earth's upper mantle is heterogeneous with respect to its O-isotope composition; (2) that both low-¹⁸O and high-¹⁸O reservoirs have contributed to basalt petrogenesis. Large-ion lithophile element-enriched basalts associated with subduction at convergent plate margins are slightly enriched in ¹⁸O, a characteristic that is considered to be an intrinsic feature of the subduction process. Intraplate oceanic and continental basalts have highly variable ¹⁸O/¹⁶O ratios, with individual localities displaying ¹⁸O ranges in excess of 1.5 to 2. Systematic co-variations between O-, Sr-, Nd-, and Pb-isotope ratios reflect the same principal intramantle end-member isotopic components (DMM, HIMU, EM-I, EM-II) deduced from radiogenic isotope considerations and, therefore, imply that a common process is responsible for the origin of upper mantle stable and radiogenic isotope heterogeneity, namely the recycling of lithospheric material into the mantle.     

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

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

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.