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.     

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.     

Mineralogical and geochemical compositions of modern bivalve shells from the Mediterranean coast of Egypt

The stable isotopic composition (¹³C and ¹⁸O) and elemental (Sr and Mg) of marine molluscs are presented for Carditacea and Solenacea shells collected off the Mediterranean coast of Egypt. Based on shell microstructures and mineralogy, the bivalve shells are preserved in their original mineralogy and chemistry.The Sr and Mg concentrations of the bivalve shells have mean values of 1960 ppm and 226 ppm respectively. The stable isotopic composition generally show high values of ¹⁸O and ¹³C. The ¹⁸O values range from +0.1 to –1.8 PDB and most shells are highly enriched in¹³C; averaging +2.5 PDB. These elemental and isotopic signatures are analogous to modern marine bivalves from other localities.The oxygen and carbon isotopes, together with the calculated temperatures, suggest that the aragonitic bivalve shells were precipitated in isotopic equilibrium from warm marine waters.     

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     

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     

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

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

Modeling of prograde mineral δ18O changes in metamorphic systems

A general model has been developed to calculate changes of ¹⁸O of minerals in addition to their composition and modal abundance in metamorphic systems. A complete set of differential equations can be written to describe any chemical system in terms of the variables dP, dT, dX, dM, and d¹⁸O (X, M, and ¹⁸O refer to the chemical composition, number of moles, and oxygen isotope composition of each phase respectively). This set is composed of the differentials of five subsets of equations: (1) conditions of heterogeneous equilibrium; (2) compositional stoichiometry for each mineral; (3) mass balance for each oxide component; (4) oxygen isotope partitioning between phases; (5) conservation of the oxygen isotope ratio of the system. The variance of the complete set of equations is 2, and changes of ¹⁸O, composition, and modal abundance for each mineral can be calculated for arbitrary changes of P and T. Applications to a typical pelitic bulk composition at amphibolite and lower granulite facies conditions suggest that for systems dominated by continuous reactions such as: (a) chlorite + quartz = garnet+H₂O; (b) staurolite + biotite = garnet + muscovite + H₂O; or (c) garnet + muscovite = sillimanite + biotite, isopleths of mineral ¹⁸O are nearly independent of pressure, and have a spacing of about 0.1 per 10–20°C. For nearly discontinuous reactions such as: (d) garnet + chlorite + muscovite = biotite + staurolite+H₂O; (e) staurolite + muscovite = biotite + aluminosilicate + garnet+H₂O; or (f) muscovite + quartz = sillimanite + K-feldspar+H₂O, isopleths of mineral ¹⁸O have slopes more nearly parallel to endmember reaction boundaries and ¹⁸O of phases can have a greater temperature dependence (e.g., 0.1 per 2°C for reaction d). This behavior results from relatively large amounts of reaction progress for small changes of P or T. However, the calculated exhaustion of a reactant within 0.1–5°C ensures that the predicted effects of such reactions on mineral ¹⁸O will not exceed 0.25 for typical bulk compositions. Models that allow for fractional crystallization of garnet suggest that prograde garnet zoning in pelitic assemblages will be relatively smooth until staurolite becomes unstable. At higher temperatures, garnet may develop a step of as much as 0.6 in its core-rim zoning as a result of combined garnet resorption during the continuous reaction garnet + muscovite = sillimanite + biotite and repartitioning of the garnet rim composition to relatively heavy ¹⁸O. The models are insensitive to the degree to which garnet fractionally crystallizes and to the isotope fractionation factors used; only extreme changes in modal abundance or bulk composition for a given mineral assemblage can produce significant changes in the predicted trends. In the absence of infiltration, isotopic shifts resulting from net transfer reactions for minerals in typical amphibolite, eclogite, and lower granulite facies metapelites and metabasites are inferred from the models to be 1 or less for 150°C of heating.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

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.     

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

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

Oxygen isotope compositions of selected laramide-tertiary granitoid stocks in the Colorado Mineral Belt and their bearing on the origin of climax-type granite-molybdenum systems

Quartz phenocrysts from 31 granitoid stocks in the Colorado Mineral Belt yield ¹⁸O values less than 10.4, with most values between 9.3 and 10.4. An average magmatic value of about 8.5 is suggested. The stocks resemble A-type granites; these data support magma genesis by partial melting of previously depleted, fluorine-enriched, lower crustal granulites, followed by extreme differentiation and volatile evolution in the upper crust.Subsolidus interaction of isotopically light water with stocks has reduced most feldspar and whole rock ¹⁸O values. Unaltered samples from Climax-type molybdenumbearing granites, however, show no greater isotopic disturbance than samples from unmineralized stocks. Although meteoric water certainly played a role in post-mineralization alteration, particularly in feldspars, it is not required during high-temperature mineralization processes. We suggest that slightly low ¹⁸O values in some vein and replacement minerals associated with molybdenum mineralization may have resulted from equilibration with isotopically light magmatic water and/or heavy isotope depletion of the ore fluid by precipitation of earlier phases.Accumulation of sufficient quantities of isotopically light magmatic water to produce measured depletions of ¹⁸O requires extreme chemical stratification in a large magma reservoir. Upward migration of a highly fractionated, volatile-rich magma into a small apical Climax-type diapir, including large scale transport of silica, alkalis, molybdenum, and other vapor soluble elements, may occur with depression of the solidus temperature and reduction of magma viscosity by fluorine. Climax-type granites may provide examples of ¹⁸O depletion in magmatic systems without meteoric water influx.     

Stable isotope (C,O, S) systematics of the mercury mineralization at Idrija,Slovenia: constraints on fluid source and alteration processes

The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the ¹³C and ¹⁸O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the ¹³C and ¹⁸O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (¹³C–4 and ¹⁸O+10), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The ³⁴S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The ³⁴S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from –19.1 to +22.8, and from –22.4 to +59.6, respectively, suggesting mixing of sulfur from different sources. The peak of ³⁴S values of cinnabar and pyrite close to 0 is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the ³⁴S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive ³⁴S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates.Editorial handling: P. Lattanzi     

Oxygen-isotope ratios in metamorphic eclogites

Rocks having O¹⁸-values less than those of normal basalts (5 to 7 permil) are very rare. However, anomalously low -values are common in European B-type eclogites, including those from N. W. Spain (1.5 to 5.6 permil), W. France, S. Germany, and W. Norway. Since isotopic exchange with sediments during metamorphism would have increased their -values, we tentatively conclude that the isotopically light eclogites descended from basaltic rocks which interacted with light meteoric waters at high temperatures, as did the Tertiary igneous rocks of W. Scotland. Isotopically heavy eclogites from S. Germany (8.6 to 10.5 permil) are isotopically similar to calc-silicate rocks from N. W. Spain and are possibly derived from dolomitic pelites.Coexisting quartz and rutile effectively fractionate the isotopes of oxygen and thereby constitute a potentially useful geothermometer. The average quartz-rutile fractionation in B-type eclogites is 6.5 permil.Lamont-Doherty Geological Observatory of Columbia University Contrib. No. 1559.     

Ion microprobe analysis of oxygen isotope ratios in granulite facies magnetites: diffusive exchange as a guide to cooling history

Ion microprobe analysis of magnetites from the Adirondack Mountains, NY, yields oxygen isotope ratios with spatial resolution of 2–8 m and precision in the range of 1 (1 sigma). These analyses represent 11 orders of magnitude reduction in sample size compared to conventional analyses on this material and they are the first report of routinely reproducible precision in the 1 per mil range for analysis of ¹⁸O at this scale. High precision micro-analyses of this sort will permit wide-ranging new applications in stable isotope geochemistry. The analyzed magnetites form nearly spherical grains in a calcite matrix with diopside and monticellite. Textures are characteristic of granulite facies marbles and show no evidence for retrograde recrystallization of magnetite. Magnetites are near to Fe₃O₄ in composition, and optically and chemically homogeneous. A combination of ion probe plus conventional BrF₅ analysis shows that individual grains are homogeneous with ¹⁸O=8.9±1 SMOW from the core to near the rim of 0.1–1.2 mm diameter grains. Depth profiling into crystal growth faces of magnetites shows that rims are 9 depleted in ¹⁸O. These low ¹⁸O values increase in smooth gradients across the outer 10 m of magnetite rims in contact with calcite. These are the sharpest intracrystalline gradients measured to date in geological materials. This discovery is confirmed by bulk analysis of 150–350 m diameter magnetites which average 1.2 lower in ¹⁸O than coarse magnetites due to low ¹⁸O rims. Conventional analysis of coexisting calcite yields °¹⁸O=18.19, suggesting that bulk ¹⁸O (Cc-Mt)=9.3 and yielding an apparent equilibration temperature of 525° C, over 200° C below the temperature of regional metamorphism. Consideration of experimental diffusion data and grain size distribution for magnetite and calcite suggests two contrasting cooling histories. The data for oxygen in calcite under hydrothermal conditions at high P(H₂O) indicates that diffusion is faster in magnetite and modelling of the low ¹⁸O rims on magnetite would suggest that the Adirondacks experienced slow cooling after Grenville metamorphism, followed by a brief period of rapid cooling, possibly related to uplift. Conversely, the data for calcite at low P(H₂O) show slower oxygen diffusion than in magnetite. Modelling based on these data is consistent with geochronology that shows slow cooling through the blocking temperature of both minerals, suggesting that the low ¹⁸O rims form by exchange with late, low temperature fluids similar to those that infiltrated the rock to serpentinize monticellite and which infiltrated adjacent anorthosite to form late calcite veinlets. In either case, the ion microprobe results indicate that two distinct events are recorded in the post-metamorphic exchange history of these magnetites. Recognition of these events is only possible through microanalysis and has important implications for geothermometry.     

Polymetamorphic relations in iron ores from the Iron Quadrangle,Brazil: The correlation of oxygen isotope variations with deformation history

This study deals with the oxygen isotope composition of hematite-rich ore bodies in the Iron Quadrangle, Brazil. The area studied can be divided into two different regions: a western (W) zone of greenschist facies assemblages and an eastern (E) zone of amphibolite facies with transitions into granulite facies assemblages.The ¹⁸O values of 136 quartz-iron oxide pairs have been determined and temperatures of formation have been calculated. The ¹⁸O values of quartz vary between +6 and 20 except one value near +23, whereas the iron oxides fall between –4 and +10, with nearly 80% of the iron oxide values between –0.5 and 4.0. The regional distribution of the ¹⁸O values is as follows: in the W-region 85% of the quartz are >12, whereas in the E-region only 46% fall in this range, In contrast to quartz the iron oxides do not show any regional differences.The variation of oxygen isotope fractionations between quartz and iron oxides is obviously related to the complex deformation history of the iron ores. Samples with a primary schistosity (S₁) only represent peak metamorphic conditions. In the E-region the (S₁) high temperatures >700° C seem to correspond to orogenic events in the Archaen basement 2,700 m.y. ago. In the W-region S₁-temperatures between 460° and 560° C seem to represent peak metamorphic conditions of the Proterozoic Minas metamorphism 2,000 m.y. ago. Iron ores which have been overprinted by later deformation events are selectively reset to lower isotopic temperatures. The more closely spaced the schistosity planes the larger the extent of a temperature lowering.The genetic processes associated with these hematite-rich ore bodies appear to be sedimentary-metamorphic rather than metasomatic processes. Furthermore, there is no evidence for secondary leaching by weathering solutions.     

Seawater-sediment-basalt interactions: stable isotope (H,O) and elemental fluxes within the Ordovician volcano-sedimentary sequence of Erquy (Brittany,France)

The Ordovician volcano-sedimentary succession of Erquy (northern Brittany) is made of immature sediments thermally metamorphosed at the contact of intruding basic sills. Pillow lavas constitute the upper part of the sequence. The trace element geochemistry of sills and pillow lavas suggests that they were derived from a tholeiitic source located beneath a passive margin. This volcanic sequence was metamorphosed under low to moderate greenschist facies conditions. In this study the direction and amplitude of chemical and isotopic fluxes in the basalt-sediment-water system were established and the oxygen and hydrogen isotope compositions of the aqueous fluid that reacted with the volcanic rocks were characterized. Cationic thermometry on chlorites and isotopic thermometry on plagioclase-chlorite pairs indicate closure metamorphic temperatures in the range 200–250°C for the basaltic sills. Stable isotope compositions of iron-rich chlorites (¹⁸O-5.5; D from-60 to-50) and plagioclases (¹⁸O from +9 to +10) reveal that the source of the fluid was certainly seawater. The ¹⁸O variations within the sills are strongly correlated with the rate of progress of the main metamorphic reaction:clinopyroxene+plagioclase+ilmenite chlorite+albite+epidote+quartz+sphene that produced major element mobility at the scale of the volcanosedimentary sequence. Calculation of elemental fluxes by mass balance combined with oxygen isotopic compositions of basalts shows that the highest water-rock ratios (1) were at sill-sediment boundaries and within pillow lavas at the top of the pile. The volcanosedimentary sequence of Erquy was a net sink for Na and a source for Ca. No Mg uptake could be detected whereas the hydrothermal alteration of the sediments released Fe, Si, and K trapped by the volcanic rocks. The ¹⁸O value of the fluid reacting with sills appears to have shifted no more than +4 after percolation at low temperature through immature sediments (¹⁸O12). The Erquy volcano-sedimentary sequence represents a marine hydrothermal system dominated by low-temperature exchange which allowed a general ¹⁸O-enrichment of the volcanic rocks and a ¹⁸O-depletion of sediments.     

The oxygen isotope composition of granitoid and sedimentary rocks of the southern Snake Range,Nevada

Six diverse intrusive igneous types are exposed as discrete outcrops within an area of 900 km² in the southern Snake Range, White Pine County, Nevada. The previously recognized variety among these igneous types is reflected in the wide range of ¹⁸O values (–1.1 to 13.4 permil) found in these rocks. This range of ¹⁸O values probably results from differences in source material and post-crystallization history of the different intrusive types.The Jurassic intrusive of the Snake Creek-Williams Canyon area represents the chemical equivalent of a large part of a differentiation sequence, with the entire range of composition (63–76 percent SiO₂) exposed over a horizontal distance of about five km. The rather regular increase of ¹⁸O values from the most mafic to the most felsic parts of this pluton, together with ¹⁸O values determined for constituent minerals recovered from five of the samples, supports a fractional crystallization model. The high ¹⁸O values found (10.2–12.2 permil) indicate that the magma likely was derived from or assimilated sedimentary materials.Nine samples of the Cretaceous two-mica granite of the Pole Canyon-Can Young Canyon area have ¹⁸O values in the range 10.6–12.1 permil. These high ¹⁸O values, an initial⁸⁷Sr/⁸⁶Sr ratio of 0.7165, and the presence of muscovite along with an accessory mineral suite limited to monazite, apatite, zircon, and an allanite-like mineral, characterize this intrusive mass as an S-type granite. It probably formed through anatexis of late Precambrian pelitic rocks.The granitoid rock exposed in the Young Canyon-Kious Basin area is Tertiary (32 m.y.). Most of this intrusive has been cataclastically deformed as a result of late (18 m.y.) movement on the overlying Snake Range decollement. The undeformed portion of this intrusive has ¹⁸O values of 8.7–10.0 permil. However, the deformed portion of this intrusive has ¹⁸O values as low as –1.1 permil, apparently resulting from isotopic exchange between this rock and ground water at the time of cataclasis.Although the igneous types exposed in the southern Snake Range differ petrologically and range in age from Jurassic to Tertiary, most have relatively high ¹⁸O values compared with other granitoid rocks of the Basin-Range Province.     

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.     

Sea water basalt interaction in spilites from the Iberian Pyrite Belt

Low grade hydrothermally metamorphosed mafic rocks from the Iberian Pyrite Belt are enriched in ¹⁸O relative to the oxygen isotopic ratio of fresh basalt (+6.5±1). The observed ¹⁸O whole rock values range from +0.87 to +15.71 corresponding to positive isotopic shifts of +5 to +10, thus requiring isotopic exchange with fluids under conditions of high water:rock ratios at low temperatures. The lowest ¹⁸O observed corresponds to an albitized dolerite still and is compatible with independent geochemical data suggesting lower water: rock ratios for the alteration of these rocks.The isotope data are consistent with the hypothesis that the spilites from the Pyrite Belt were produced by interaction of basaltic material with sea water.Significant leaching of transition metals from the mafic rocks during alteration coupled with available sulphur isotopic data for the sulphide ores also suggest that sea water may have played an important role in the formation of ore deposits in the Iberian Pyrite Belt.     

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.