A geochemical and stable isotope study of some rocks from the Bandelierkop formation, southern marginal zone of the Limpopo Belt, South Africa( vol.1 Text)

The Bandelierkop Formation of the Southern Marginal Zone (SMZ) of the Limpopo Belt consists of metamorphosed ultramafic, mafic and sedimentary rocks. Metamorphic conditions indicated by the petrography of these different rock groups are consistent with upper amphibolite to granulite facies. The ultramafic and mafic rocks are geochemically akin to peridotitic-pyroxenitic intrusive rocks and high-Mg basalts respectively. Metamorphism of these two rock groups in the SMZ was an essentially closed system process, except for the highly volatile phases such as H₂O and CO₂. The metasediments appear to represent a sequence of high (Mg+Fe)-greywackes and/or deep-water shales with minor amounts of iron formation material. The unusually mafic character of the metasediments can be ascribed to a high ultramafic + mafic source component to the original sediment. Some modification of the major and trace element compositions of the pelitic rocks has been caused by the removal of partial melts and the metamorphism of the pelitic rocks is not therefore considered to have occurred under closed system conditions. Variable extraction of partial melts is implied by the chemical variations shown by the pelitic rocks and is also suggested by the presence of large pegmatitic felsic bodies which are commonly found close to the pelitic rocks. Detailed petrographic study of the Bandelierkop Formation rocks suggests an increase in metamorphic grade, and/or a decrease in water activity, from south to north within the Southern Marginal Zone. Peak metamorphic conditions of 730°C + 65°C at pressures of 6.1 ± 1.5 kbars may be deduced from a careful application of several cation thermometers and barometers on selected mineral analyses. A rigorous application of garnet-biotite thermometry to the pelitic rocks indicates that the transition from orthoamphibole gneisses in the south to orthopyroxene-bearing rocks in the north of the SMZ terrane, is a function of changing biotite composition and/or decreasing water activities rather than an increase in metamorphic temperatures. In contrast to the major and trace element data, the stable isotope data for the ultramafic and mafic rocks in the SMZ indicate open system behaviour for some of these rocks, but closed system behaviour for the pelites. Extraction of SO to 70% partial melts from the pelitic rocks, should not, however, have affected the δ¹⁸O value of the restite. Petrological and stable isotope data in the SMZ rocks are consistent with retrogression in all these rocks and open system behaviour for oxygen in some ultramafic and mafic rocks, being caused by the crystallization and accompanying fluid release of melts produced during prograde metamorphism of the pelitic rocks. Small scale (-5 to 30m's) heterogeneity is implied by both oxygen and carbon stable isotope compositions of closely spaced rock samples, even for those collected from within large "shear zones", suggesting small fluid/rock ratios for most of the samples in the high-grade terrane or heterogeneous stable isotopic compositions of the fluids. Furthermore, a similarity in mineral-mineral stable isotope fractionation factors is observed for all the pelitic rocks, including the orthoamphibole gneisses found immediately south of the orthopyroxene isograd. These features preclude the presence of pervasive fluid infiltration after peak metamorphism. Two implications are, that granulite facies metamorphism in the SMZ terrane was not caused by an influx of mantle derived CO₂-rich fluid and, that the orthoamphibole gneisses are not retrogressed equivalents of the granulites found to the north of the orthopyroxene isograd. It is suggested that this isograd represents a change in the water activities of the rocks during metamorphism. Apparent disequilibria in mineral - mineral stable isotope fractionations observed amongst different minerals within any one pelitic rock, may be explained by a combination of the crystallization of residual melt within these rocks and oxygen diffusion amongst minerals which have not reached their oxygen-closure. The concordant quartz-plagioclase, quartz-biotite and plagioclase-biotite oxygen isotope equilibration temperatures are taken to represent minimum crystallization temperatures for the melts (-560°C), while successively higher quartz-orthopyroxene, quartz-amphibole and quartz-garnet oxygen isotope equilibration temperatures are a function of increasing closure temperatures for the orthopyroxene, amphibole and garnet respectively. The minimum estimate to peak metamorphic temperatures is given by the quartz-garnet oxygen isotope temperature averaging 736 + 52°C. If oxygen diffusion experiments performed in hydrothermal systems are appropriate for the SMZ rocks, then cooling rates for the SMZ terrane could have been as low as 12 to 25°C/My over a temperature range of 480 to 600°C. Stable isotope modeling of hypothetical fluids that may have been in equilibrium with the high-grade rocks, suggests that a mixture of CO₂ and H₂O, with CO₂/H₂O mole ratios > 0.1 can precipitate both quartz and carbonate of stable isotope composition similar to those determined for quartz and carbonate from the mineralized Archaean lode gold deposits of the Murchison and Pietersburg greenstone belts. A model involving granulite facies metamorphism, partial melt extraction and subsequent release of fluids, Au, K and S upon crystallization of such melts, appears to be viable for gold mineralization occuring in the adjacent lower grade greenstone belts and in the high-grade terrane of the Southern Marginal Zone

Stable isotope ecology of Miocene large mammals from Sandelzhausen, southern Germany

The carbon, oxygen, and strontium isotope composition of enamel from teeth of large Miocene herbivorous mammals from Sandelzhausen (MN5, late Early/early Middle Miocene) in the North Alpine foreland basin, were analyzed to infer diet and habitat. The mean enamel δ13C value of −11.4±1.0‰ (n=53) for the nine taxa analyzed (including proboscideans, cervids, suids, chalicotheres, equids, rhinocerotids) indicates a pure C3 plant diet for all mammals. 87Sr/86Sr ratios of ~0.710 higher than those from teeth of the western Molasse Basin (0.708-0.709) seem to indicate preferential feeding of the mammals in the northeastern Molasse Basin. The sympatric herbivores have different mean δ13C and δ18O values which support diet partitioning and/or use of different habitats within a C3 plant ecosystem. Especially the three sympatric rhinoceroses Plesiaceratherium fahlbuschi, Lartetotherium sansaniense, and Prosantorhinus germanicus show clear partitioning of plants and/or habitats. The palaeomerycid Germanomeryx fahlbuschi was a canopy folivore in moderately closed environments whereas Metaschizotherium bavaricum (Chalicotheriidae) and P.germanicus (Rhinocerotidae) were browsers in more closed forest environments. The horse Anchitherium aurelianense was probably a more generalized feeder than assumed from its dental morphology. The forest hog Hyotherium soemmeringi has the highest δ13C and lowest δ18O value of all analyzed taxa, possibly related to a frugivorous diet. Most taxa were water-dependent browsers that record meteoric water δ18O values of about −5.6±0.7‰ Vienna Standard Mean Ocean Water (VSMOW). Using a modern-day mean annual air temperature (MAT)-$$\delta^{18} {\text{O}}_{{{\text{H}}_{ 2} {\text{O}}}}$$ relation a MAT of 19.3±1.5°C can be reconstructed for Sandelzhausen. A Gomphotherium subtapiroideum tusk serially sampled for δ18O values does not record a clear pattern of seasonality. Thus most taxa were C3 browsers in a forested and humid floodplain environment in the Molasse Basin, which experienced a warm-temperate to subtropical climate and possibly low seasonalit

Sediment penetration depths of epi- and infaunal ostracods from Lake Geneva (Switzerland)

Many (palaeo-)environmental parameters can be deduced from ecological and chemical analyses of ostracods. However, the specific ecology of each taxon has a great impact on its reaction to changing environmental conditions. As a consequence, each taxon records these changes differently. The mean penetration depth (MPD) and relative individual abundances have been documented along sediment depth profiles for the dominant sub-littoral to profundal species of ostracods in western Lake Geneva, Switzerland, and this data can be used to estimate their preferential habitat in terms of sediment depths. Isocypris beauchampi, Limnocytherina sanctipatricii, Cypria ophtalmica forma lacustris at 13-m water depths, Limnocythere inopinata, and a winter generation of Herpetocypris reptans have the shallowest habitat preferences at the study sites (MPDs of 0.45, 0.48, 0.49, 0.60, and 0.81cm, respectively). These results suggest that these populations may be regarded as being preferentially epifaunal forms. Populations of Cytherissa lacustris (MPDs of 0.61, 0.73, and 0.82cm at 13-, 33-, and 70-m water depths, respectively), Cypria ophtalmica forma lacustris at 70m (MPD=0.96cm), Fabaeformiscandona caudata (MPD=0.99cm), and a summer generation of Herpetocypris reptans (MPD=1.03cm) were identified as being infaunal. Candona neglecta is the species that was found the deepest in the sediment of Lake Geneva, with MPDs of 0.65, 1.22, and 1.30cm at 13-, 33-, and 70-m water depths, respectively. Information on the sediment texture and oxygen concentrations inferred from the analyses of sediment pore water suggest that the oxygen content of the sediment pore water is not the only dominant parameter controlling the differences in ostracod sediment penetration depths observed among the different sites, but that they might also be influenced by the sediment ‘softness,' which itself depends on grain size, water content, and the abundance of organic matter in sedimen

Stable isotope compositions of the Penninic ophiolites of the Kõszeg-Rechnitz series

Abstract The ophiolitic rocks of the easternmost Penninic unit, the Kőszeg-Rechnitz series, were analyzed for their H, C and O stable isotope compositions. Serpentinite, gabbro, blueschist, talc deposits, ophicarbonates, as well as calcite and inclusion fluids from quartz segregation veins were analyzed in order to determine the effects of different metamorphic events on the stable isotope compositions. The oxygen isotope compositions have a wide range depending on rock type and locality. Gabbro and serpentinite of Bienenhütte (Bernstein Window) have preserved mantle-like δ18O values (5.9 to 6.3‰; all values are in ‰ relative to V-SMOW), whereas the serpentinite of Glashütten and Rumpersdorf (Kőszeg-Rechnitz Window) and the silicate minerals of the ophicarbonate rocks show a strong 18O-enrichment (up to 16.2‰). The 18O-enrichment may have been induced by low-temperature serpentinization or interaction with 18O-rich fluids that had been in equilibrium with sedimentary rocks. Contrary to the O isotope compositions, the H isotope compositions seem to be homogeneous in the entire series, with D values of −63 ± 7‰. Only some serpentinite rocks were depleted in D (down to −106‰), usually regarded as a result of interaction with meteoric water infiltrating during late-stage metamorphism. The meteoric water infiltration was rather limited, as even samples taken directly from slickensides within serpentinite bodies preserved isotopic compositions close to those of the bulk series. H and O isotope compositions of fluids mobilized in the metasedimentary rocks of the Penninic unit during the main metamorphic stage were determined by analyzing inclusion fluids and calcites in quartz-carbonate veins. The isotope compositions indicate interaction between these fluids and the ophiolite series, although relative deuterium enrichment has been preserved in the ophiolitic rocks. The strong D-enrichment characteristic for oceanic crust that has experienced high-temperature interaction with seawater was not detected. However, the H isotope compositions obtained for the Kőszeg-Rechnitz series indicate that subduction of the Penninic oceanic crust and the associated devolatilization may have been potentially responsible for mantle metasomatism, resulting in H isotope compositions of about −40‰, similar to the range determined from mantle-derived amphibole megacrysts (Demény et al. 2005). To conclude, the present dataset is discussed in the light of earlier studies on the formation of the Sopron leucophyllite

The Grønnedal-Ika Carbonatite-Syenite Complex, South Greenland: Carbonatite Formation by Liquid Immiscibility

The Grønnedal-Ika complex is dominated by layered nepheline syenites which were intruded by a xenolithic syenite and a central plug of calcite to calcite-siderite carbonatite. Aegirine-augite, alkali feldspar and nepheline are the major mineral phases in the syenites, along with rare calcite. Temperatures of 680-910°C and silica activities of 0·28-0·43 were determined for the crystallization of the syenites on the basis of mineral equilibria. Oxygen fugacities, estimated using titanomagnetite compositions, were between 2 and 5 log units above the fayalite-magnetite-quartz buffer during the magmatic stage. Chondrite-normalized REE patterns of magmatic calcite in both carbonatites and syenites are characterized by REE enrichment (LaCN-YbCN = 10-70). Calcite from the carbonatites has higher Ba (∼5490 ppm) and lower HREE concentrations than calcite from the syenites (54-106 ppm Ba). This is consistent with the behavior of these elements during separation of immiscible silicate-carbonate liquid pairs. εNd(T = 1·30 Ga) values of clinopyroxenes from the syenites vary between +1·8 and +2·8, and εNd(T) values of whole-rock carbonatites range from +2·4 to +2·8. Calcite from the carbonatites has δ18O values of 7·8 to 8·6‰ and δ13C values of −3·9 to −4·6‰. δ18O values of clinopyroxene separates from the nepheline syenites range between 4·2 and 4·9‰. The average oxygen isotopic composition of the nepheline syenitic melt was calculated based on known rock-water and mineral-water isotope fractionation to be 5·7 ± 0·4‰. Nd and C-O isotope compositions are typical for mantle-derived rocks and do not indicate significant crustal assimilation for either syenite or carbonatite magmas. The difference in δ18O between calculated syenitic melts and carbonatites, and the overlap in εNd values between carbonatites and syenites, are consistent with derivation of the carbonatites from the syenites via liquid immiscibilit

Potential influence of the chemical composition of water on the stable oxygen isotope composition of continental ostracods

Many studies in continental areas have successfully used the oxygen isotope composition of fossil ostracod valves to reconstruct past hydrological conditions associated with large changes in climate. Yet, ostracods are known to crystallise their valves out of isotopic equilibrium for oxygen and they generally have higher 18O contents compared to inorganic calcite grown at equilibrium under the same conditions. A review of vital offsets determined for continental ostracods indicates that vital offsets might change from site to site, questioning a potential influence of environmental conditions on oxygen isotope fractionation in ostracods. Results from the literature suggest that pH has no influence on ostracod vital offset. A re-evaluation of results from Li and Liu (J Paleolimnol 43:111-120, 2010) suggests that salinity may influence oxygen isotope fractionation in ostracods, with lower vital offsets for higher salinities. Such a relationship was also observed for the vital offsets determined by Chivas et al. (The ostracoda—applications in quaternary research. American Geophysical Union, Washington, DC, 2002). Yet, when results of all studies are compiled, the correlation between vital offsets and salinity is low while the correlation between vital offsets and host water Mg/Ca is higher, suggesting that ionic composition of water and/or relative abundance of major ions may also control oxygen isotope fractionation in ostracods. Lack of data on host water ionic composition for the different studies precludes more detailed examination at this stage. Further studies such as natural or laboratory cultures done under strictly controlled conditions are needed to better understand the potential influence of varying environmental conditions on oxygen isotope compositions of ostracod valve

Studying the dynamic of a high alpine catchment based on multiple natural tracers

Hydrological processes in high elevation catchments are largely influenced by snow accumulation and melt, as well as summer rainfall input. The use of the stable isotopes of water as a natural tracer has become popular over recent years to characterize water flow paths and storage in such environments, in conjunction with electric conductivity (EC) and water temperature measurements. In this work, we analyzed in detail the potential of year round samples of these natural tracers to characterize hydrological processes in a snow-dominated Alpine catchment. Our results underline that water temperature measurements in springs, groundwater and in-stream are promising to trace flow path depth and relative flow rates. The stable isotopes of water are shown here to be particularly valuable to get insights into the interplay of subsurface flow and direct snowmelt input to the stream during winter and early snow melt periods. Our results underline the critical role of subsurface flow during all melt periods and the presence of snowmelt even during winter base flow. We furthermore discuss why reliably detecting the role of subsurface flow requires year-round water sampling in such environments. A key conclusion of our work is the added value of soil and water temperature measurements to interpret EC and isotope analyses, by giving additional information on snow-free periods and on flow path depths

A simple and inexpensive method of hydrogen isotope and water analyses of minerals and rocks based on zinc reagent

A new method based on Zn reagent for the quantitative conversion H2O to H2 for the hydrogen isotope analysis of hydrous minerals and whole rocks has been developed. Analyses by this method are of comparable accuracy and precision (~ 1[per mille sign]; 2O) to those of conventional extraction methods based on uranium reagent and is significantly simpler, faster and less expensive.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/31007/1/0000682.pd