Liquid composition-dependence of calcium isotope fractionation during diffusion in molten silicates

Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 °C and P = 1.0 GPa for durations of 12-24 h in a standard piston-cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but ⁴⁴Ca/⁴⁰Ca variations of ca. 5‰ arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients.A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al₂O₃, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models.     

Benthic species as mud patrol - modelled effects of bioturbators and biofilms on large-scale estuarine mud and morphology

Sediment-stabilizing and -destabilizing organisms, i.e. microphytobenthos (biofilms) and macrozoobenthos (bioturbators), affect the erodibility of muddy sediments, potentially altering large-scale estuarine morphology. Using a novel eco-morphodynamic model of an idealized estuary, we investigate eco-engineering effects of microphytobenthos and two macrozoobenthic bioturbators. Local mud erodibility is based on species pattern predicted through hydrodynamics, soil mud content, competition and grazing. Mud resuspension and export is enhanced under bioturbation and prevented under biostabilization through respective exposure and protection of the supra- and intertidal. Bioturbation decreases mud thickness and bed elevations, which increases net mud fluxes. Microphytobenthos reduces erosion, leading to a local mud increase of intertidal sediments. In multi-species scenarios, an effective mud-prone bioturbator strongly alters morphology, exceeding that of a more abundant sand-prone moderate species, showing that morphological change depends on species traits as opposed to abundance. Altering their habitat, the effective mud-prone bioturbator facilitates expansion of the sand-prone moderate bioturbator. Grazing and species competition favor species distributions of dominant bioturbators. Consequently, eco-engineering affects habitat conditions while species interactions determine species dominance. Our results show that eco-engineering species determine the mud content of the estuary, which suggests large effects on the morphology of estuaries with aggravating habitat degradation.     

The genetic relationship between mafic dike swarms and plutonic reservoirs in the mesozoic of central chile (30°–33°45′S): insights from AMS and geochemistry

Five mafic dike swarms between 30° and 33°45′S were studied for their geochemical signature and kinematics of magma flow directions by means of AMS data. In the Coastal Range of central Chile (33°−33°45′S), Middle Jurassic dike swarms (Concón and Cartagena dike swarms, CMDS and CrMDS, respectively) and an Early Cretaceous dike swarm (El Tabo Dike Swarm, ETDS) display the presence of dikes of geochemically enriched (high-Ti) and depleted (low-Ti) basaltic composition. These dikes show geochemical patterns that are different from the composition of mafic enclaves of the Middle Jurassic Papudo-Quintero Complex, and this suggests that the dikes were injected from reservoirs not related to the plutonic complex. The mantle source appears to be a depleted mantle for Jurassic dikes and a heterogeneous-enriched lithospheric mantle for Cretaceous dikes. In the ETDS, vertical and gently plunging magma flow vectors were estimated for enriched and depleted dikes, respectively, which suggest, together with variations in dike thickness, that reservoirs were located at different depths for each dike family. In the Elqui Dike Swarm (EDS) and Limarí Mafic Dike Swarm (LMDS), geochemical patterns are similar to those of the mafic enclaves of the Middle Jurassic plutons. In the LMDS, east to west magma flow vectors are coherent with injection from neighbouring pluton located to the east. In the EDS, some dikes show geochemical and magma flow patterns supporting the same hypothesis. Accordingly, dikes do not necessarily come from deep reservoir; they may propagate in the upper crust from coeval shallow pluton chamber. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

Iron in plagioclase as a monitor of the differentiation of the Skaergaard intrusion

Several recent publications suggest that the appearance of Fe-Ti oxides terminates iron enrichment and starts pronounced silica enrichment (the Bowen trend) during the differentiation of tholeiitic basalt. However, this does not appear to hold for the Skaergaard intrusion. New data from a ∼950 m long drill core (90–22) through its Upper Zone reveal that: (1) iron in plagioclase increases from ∼0.25 to ∼0.45 wt% FeO_T with fractionation of evolved oxide ferrodiorites (An_46-32) and (2) the evolving liquid, which is modelled by incremental bulk-rock summation, increased its iron content from 20.1 to 26.5 wt% FeO_T and its silica content from 47.4 to 49.6 wt% SiO₂ with fractional crystallisation (the Fenner trend). Positive correlation between modelled iron-content of the magmas, and measured iron-content of plagioclase, confirms that iron enrichment is petrologically feasible even with Fe-Ti oxides in the fractionating assemblage. As suggested by previous authors, fractional crystallisation closed to oxygen exchange is the likely reason why some layered intrusions diverge from the Bowen mechanism of differentiation. It is emphasised that both trends seem to exist in nature. Received:13 May 1996 / Accepted:5 January 1997     

Environmental changes in an alpine lake (Gossenköllesee, austria) over the last two centuries – the influence of air temperature on biological parameters

Changes in microfossils (diatoms, chrysophytes, chironomids and cladocera remains), geochemistry and deposition of atmospheric pollutants have been investigated in the sediment records of the alpine lake Gossenköllesee (Tyrol, Austria) spanning the last two centuries. The sediment records were compared with seasonal and annual air temperature trends calculated for the elevation (2417 m a.s.l.) and the geographical position (47° 1346N, 11° 0051E) of the lake, and with precipitation records available since 1866 from Innsbruck. Temperature trends followed a 20–30 year oscillation between cold and warm periods. Regarding long-term changes, temperature trends showed a U-shaped trend between 1780 and 1950, followed by a steep increase since 1975.Physical, geochemical, and organic parameters were not controlled by air temperature. Among the biological records only diatoms and chrysophytes reacted to air temperature changes: the relative abundance of planktonic diatoms increased during warm periods and changes in mean annual alpine air temperature explained 36.5% of their variation. The relation between abundance of seasonal stomatocyst types and air temperature varied on two different time scales: while summer stomatocysts were influenced by short term temperature fluctuations, the autumn stomatocysts were affected only by the long term changes. Other biological parameters exhibited a constant species composition (chironomids, pigments) or changes were small and independent of temperature (cladocera). Spheroidal carbonaceous fly-ash particles, and trends in Pb and Cr indicated increasing deposition of atmospheric pollutants but had no detectable effects on the biological parameters either. In respect to temperature variations over the last 200 years, this alpine lake is much less sensitive than expected and has thus to be regarded as a well buffered site. However, temperature alone is not sufficient to understand changes in species composition and other biogeochemical processes with unknown historical patterns might have affected species composition more strongly.     

The Importance of Microbial Iron Sulfide Oxidation for Nitrate Depletion in Anoxic Danish Sediments

Nitrate (NO₃ ^?) reduction processes are important for depleting the NO₃ ^? load from agricultural source areas before the discharge water reaches surface waters or groundwater aquifers. In this study, we experimentally demonstrate the co-occurrence of microbial iron sulfide oxidation by NO₃ ^? (MISON) and other NO₃ ^?-depleting processes in a range of contrasting sediment types: sandy groundwater aquifer, non-managed minerotrophic freshwater peat and two brackish muddy sediments. Approximately 1/3 of the net NO₃ ^? reduction was caused by MISON in three of the four environments despite the presence of organic carbon in the sediment. An apparent salinity limitation to MISON was observed in the most brackish environment. Addition of high surface area synthetically precipitated iron sulfide (FeS _x ) to the aquifer sediment with the lowest natural FeS _x reactivity increased both the relative fraction of NO₃ ^? reduction linked to MISON from approximately 30–100 % and the absolute rates by a factor of 17, showing that the potential for MISON-related NO₃ ^? reduction is environmentally significant and rate limited by the availability of reactive FeS _x .     

Geochemistry of magnesites and dolomites at the Oberdorf/Laming (Austria) deposit and implications for their origin

The major and trace element geochemistry of magnesite and dolomite samples from alternating rock masses at the Oberdorf/Laming (Styria, Austria) mineralization has been studied. The rare earth elements (REE) are considered to be of importance for the discussion of the origin of sparry magnesite deposits. The Al and REE contents are positively correlated, indicating a clay component as the main source for REE in the magnesites and their precursor rocks. Our data support the view that the Oberdorf and probably other magnesite mineralizations in the Eastern Alps have been formed by metasomatism. Through this process calcite (which was deposited by sedimentation in a marine environment) underwent dolomitization. Subsequently, Mg-rich solutions circulating through the rock masses formed the magnesite bodies.During the formation of the dolomites and the conversion to magnesites, the REE patterns of the original carbonates remained unchanged. The magnesites exhibit patterns that are very similar to sedimentary carbonates (which contain a REE-bearing clay component). Magnesites of purely sedimentary origin, formed in a predominantly evaporitic environment, should have lower total REE contents and different patterns due to the short residence times of these elements in seawater. Analyses of talc pseduomorphs after magnesite indicate as well that the REE patterns are not significantly altered during the talcification. The Mg-rich solutions that led to the formation of the magnesites have probably been derived from serpentinites below the gneiss complexes of eastern Styria and the South Penninic units of the Tauern window.

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Zusammenfassung Die Haupt- und Spurenelementgeochemie von Magnesit- und Dolomitproben, die aus alternierenden Gesteinsstöcken in der Magnesitmine von Oberdorf/Laming (Steiermark, Österreich) stammen, wurde untersucht. Besonderes Augenmerk wurde dabei auf die Geochemie der Seltenen Erdelemente (REE) gelegt, da diese für Aussagen über die Entstehung der Magnesitlagerstätten von besonderer Bedeutung sind. Eine positive Korrelation zwischen den Al und REE-Gehalten deutet darauf hin, daß der Hauptteil der REE einer Tonkomponente entstammt. Die Daten unterstützen eine metasomatische Entstehung der Spatmagnesite der Oberdorfer Lagerstätte und anderer Ostalpiner Lagerstätten. Sedimentär angelegter Kalzit wird dabei über Dolomit mit Mg-reichen Lösungen in Magnesit umgewandelt.Während der Metasomatose bleiben die chondritnormierten REE-Verteilungen der Ausgangskarbonate relativ unverändert erhalten. Die so entstandenen Spatmagnesite weisen Verteilungsmuster auf, die jenen der sedimentären Karbonate, aus denen sie entstanden sind, entsprechen. Rein sedimentär entstandene Magnesite werden praktisch nur in evaporitischem Milieu gebildet und sollten infolge der kurzen Verweilzeit dieser Elemente im Meerwasser wesentlich niedrigere REE-Gehalte und andere Verteilungsmuster aufweisen. Analysen einer Talkpseudomorphose zeigen, daß sich die REE-Verteilungsmuster auch bei der metasomatischen Talk-bildung nicht wesentlich ändern. Die Mg-reichen Lösungen, die zur Bildung der Magnesite notwendig waren, entstammen vermutlich tiefliegenden Sepentiniten, auf die es Hinweise im Untergrund der oststeirischen Gneisskomplexe und des südpenninischen Tauernfensters gibt.

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Résumé Cette note présente les résultats d'une étude géochimique des éléments majeurs et en trace d'échantillons de magnésite et de dolomite qui se présentent en masses alternées dans la mine de magnésite de Oberdorf/Laming (Steiermark, Autriche). Une attention particulière a été apportée aux terres rares, considérées comme fournissant des arguments importants dans la discussion de l'origine des gisements. Les teneurs en Al et en terres rares montrent une corrélation positive, ce qui permet de rapporter à un composant argileux la source principale des terres rares. Les résultats obtenus plaident en faveur d'une origine métasomatique des minéralisations en magnésite d'Oberdorf et d'autres endroits des Alpes orientales. Au cours de ce processus, la calcite, d'origine sédimentaire marine, a été le siège d'une dolomitisation avec, subséquemment, formation de corps de magnésite grâce à la circulation de solutions riches en Mg.Au cours de la métasomatose, la distribution des terres rares des carbonates originels n'est pas modifiée: les magnésites montrent des répartitions très semblables à celles des carbonates sédimentaires (lesquels renferment un constituant argileux porteur des terres rares). Des magnésites d'origine purement sédimentaires, formées en milieu évoporitique, doivent présenter un contenu total en terres rares moins élevé et une distribution différente de ces éléments, eu égard à la brièveté de leur séjour dans l'eau de mer. Des analyses de pseudomorphoses de magnésite en talc montrent de même que la distribution des terres rares n'est pas modifiée de manière significative au cours de la talcification. Les solutions riches en Mg responsables de la formation de la magnésite sont probablement dérivées de serpentines situées sous les complexes gneissiques de Styrie et les unités penniques méridionales de la fenêtre des Tauern.

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Metal fluxes to the sediments of the Moulay Bousselham lagoon,Morocco

The metal content in surface sediments (0–2 cm, 26 samples), in a sediment core (120, 1 cm slices), taken from Moulay Bousselham (Morocco) was investigated. Concentrations of Al, Fe, Mn, Pb, Zn, Cu, Ni, Cr, Cd, As, and Hg were evaluated in surface and cored sediments of Moulay Bousselham lagoon. Significantly high concentrations in μg g⁻¹ dw of Pb (31.7–6.2), Zn (758.9–167), Cu (310.7–22), Ni (96–10.5), Cr (113–18.9), Cd (0.84–0.02), As (1–0.1), and Hg (0.61–0.02) were found in sediment samples from Moulay Bousselham lagoon. Calculated enrichment factors [EF_Me = (Me/Al)_sample/(Me/Al)_background], using Al as a normalizer, and correlation matrices showed that metal pollution in Merja Zerga of Moulay Bousselham lagoon was the product of anthropogenic sources, while the metal content in Merja Kehla was of natural origins. The results suggest that a major change in the sedimentary regime of the lagoon, associated with internal trapping and re-distribution of heavy metal, has been occurring in the past few decades. The cause would appear to be the construction of a Nador Canal at the lagoon. Probable effects concentrations (PEC) were often exceeded for heavy metals in the lagoon sediments, especially for Zn, Cu, Ni, and Cr, and four stations, stations MZ-11, MZ-12, MZ-13, MZ-14, MZ-16, and MZ-17, had multiple metals at presumptively toxic levels. These comparisons suggest that sediment metal levels in the river are clearly high and probably pose an environmental risk at some stations. The levels of most of the metals were not greatly enriched, a consideration that is of the utmost importance when contamination issues are at stake. Metal concentrations found in Moulay Bousselham lagoon were comparable to aquatic systems classified as contaminated from other regions of the world.