Effect of pressure, temperature, and oxygen fugacity on the metal-silicate partitioning of Te, Se, and S: Implications for earth differentiation

We have measured liquid Fe metal-liquid silicate partitioning (D_i) of tellurium, selenium, and sulfur over a range of pressure, temperature, and oxygen fugacity (1-19 GPa, 2023-2693 K, fO₂ −0.4 to −5.5 log units relative to the iron-wüstite buffer) to better assess the role of metallic melts in fractionating these elements during mantle melting and early Earth evolution. We find that metal-silicate partitioning of all three elements decreases with falling FeO activity in the silicate melt, and that the addition of 5-10 wt% S in the metal phase results in a 3-fold enhancement of both D_Te and D_Se. In general, Te, Se, and S all become more siderophile with increasing pressure, and less siderophile with increasing temperature, in agreement with previous work. In all sulfur-bearing experiments, D_Te is greater than D_Se or D_S, with the latter two being similar over a range of P and T. Parameterized results are used to estimate metal-silicate partitioning at the base of a magma ocean which deepens as accretion progresses, with the equilibration temperature fixed at the peridotite liquidus. We show that during accretion, Te behaves like a highly siderophile element, with expected core/mantle partitioning of >10⁵, in contrast to the observed core/mantle ratio of ∼100. Less extreme differences are observed for Se and S, which yielded core/mantle partitioning 100- to 10 times higher, respectively, than the observed value. Addition of ∼0.5 wt% of a meteorite component (H, EH or EL ordinary chondrite) is sufficient to raise mantle abundances to their current level and erase the original interelement fractionation of metal-silicate equilibrium.     

A morphological, sedimentological and geophysical investigation of the Woore Moraine, Shropshire, England

The Bar Hill-Whitchurch-Wrexham Morainic Complex is a large-scale glacial landform thought to represent either the maximum extent or the re-advance of the British-Irish Ice Sheet during the Late Devensian. The origin of the moraine remains uncertain as its key characteristics have not been studied in detail due to a lack of exposures from which its large-scale structure can be determined. The development of new technologies has enabled detailed examination of the topography and internal structure of such large-scale landforms. This paper describes a multi-disciplinary approach involving digital geomorphological mapping using enhanced resolution NextMAP™ digital surface models, geophysical imaging (electrical resistivity tomography) and conventional sedimentological analyses. This combination of techniques is useful for elucidating the origin of a large glacial landform in a region of poor exposure. Digital elevation models such as NextMAP™ offer an efficient and accurate method for landform-mapping, whilst electrical resistivity tomography was able to map the major constituent sediments of the moraine, which had in turn been identified in the single exposure available. Additional geophysical techniques should however be applied to provide further structural data and thereby enable a more detailed interpretation of the moraine's internal structure. Preliminary findings indicate that the moraine is a glaciotectonic landform composed of diamicton and glaciofluvial sediments, an origin consistent with recent suggestions that the Cheshire Plain contained an active ice lobe during the last glacial maximum.     

On the breakdown of zircon upon “dry” thermal annealing

Zircon samples without and with secondary chemical alteration from diverse sources were subjected to heat treatment at 1400 °C for 96 h. Resulting new phases and textures suggest that decomposition of zircon into component oxides occurred in all experiments to various degrees. The crucible material was found to have a strong influence on the extent of breakdown, especially in the case of altered starting materials. In this study the progressive stages of the breakdown of zircon grains are described. The factors that may govern the decomposition are discussed, including radiation damage, secondary alteration and external reaction conditions (sample container, atmosphere). Alumina crucibles should generally be avoided in dry annealing of zircon, to minimise uncontrolled breakdown into oxides.     

The bimodal rift-related Juscelândia volcanosedimentary sequence in central Brazil: Mesoproterozoic extension and Neoproterozoic metamorphism

The Barro Alto Complex and Juscelândia volcanosedimentary sequence are exposed in the central part of the Neoproterozoic Brasília belt of central Brazil. The former is a large (approximately 150 km long), boomerang-shaped, mafic-ultramafic, layered complex formed by two different intrusions metamorphosed under granulite facies. These rocks are tectonically overlain by rocks of the Juscelândia volcanosedimentary sequence, represented mainly by biotite-gneiss and amphibolite, or amphibolite facies metamorphic equivalents of rhyolite and basalt, respectively. New SIMS U–Pb zircon data and Sm–Nd isochron data presented herein help clarify the igneous and metamorphic evolution of the Juscelândia volcanosedimentary sequence, as well as its relationship with the Barro Alto Complex. Zircon grains from two biotite gneisses were analyzed by SIMS (SHRIMP) and indicate Mesoproterozoic dates, approximately 1.28 Ga, interpreted as the time of bimodal volcanism in a tectonic setting transitional between a continental rift and an ocean basin. Metamorphism is constrained by Sm–Nd garnet-whole-rock isochrons for garnet amphibolite and pelitic schists of the Juscelândia sequence, as well as for clinopyroxene-garnet amphibolite and garnet granulite of the Barro Alto Complex, which give ages between 0.74 and 0.76 Ga, in agreement with SIMS dates for metamorphic zircon rims. These new data are significant, because they establish that a single metamorphic event affected both the Barro Alto Complex and the Juscelândia sequence. Based on these new data, we present a modified tectonic model for the Brasília belt.     

Trophic relationships of three sunfishes (Lepomis spp.) in an estuarine bayou

We examined ontogenetic, interspecific, and seasonal trophic patterns among sympatric sunfish species, redspotted sunfish,Lepomis miniatus; redear sunfish,Lepomis microlophus; and bluegill,Lepomis macrochirus, in an estuarine bayou. In particular we studied these feeding patterns in relation to relative abundances of prey from different benthic feeding habitats. All three sunfishes showed ontogenetic divergence in their trophic niches, reflecting different ecomorphological specializations. Small fishes depended on zooplankton, whereas larger fishes of all three species shifted their diets to benthic macrofauna. A potential for trophic resource partitioning was reflected by dietary differences among the three sunfish species. One impalied mechanism for resource partitioning was feeding habitat, as redear sunfish frequently used sediment-associated prey, while bluegill showed greater use of water-column-associated prey, and redspotted sunfish often used SAV-associated prey. However, all three sunfishes apparently used each feeding habitat to some degree; and, trophic differences were more clearly based on prey type than on feeding habitat. Redear sunfish, which can crush hard-shelled prey, exhibited the most distinctive diet. An apparent seasonal shift in feeding habitat occurred in autumn/winter, as indicated by increased overlap between diets and SAV. This shift was facilitated by changes in the relative abundances of several common prey types between benthic habitats. The relative abuandance and use of freshwater and estuarine-derived prey also varied seasonally, suggesting a possible trophic benefit of consistent prey availability in the estuarine bayou.     

Influence of ambient flow around the horseshoe crabLimulus polyphemus on the distribution and orientation of selected epizoans

Cumulatively scored distributions of the slipper shell gastropodCrepidula sp., the sand-building polychaete wormSabellaria vulgaris, the calcareous meandering tubed polychaeteFilograna implexa, the barnacleSemibalanaus balanoides, and the lacy bryozoanSchizoporella sp. were mapped on a cm-square gridded silhouette of the prosoma, opisthosoma, and movable spines, and telson of the horseshoe crabLimulus polyphemus stranded on Reeds Beach, Cape May County, New Jersey in the Delaware Bay. Statistically tested and contoured epizoan frequencies for 81 males and 59 females revealed that slipper shells and agglutinated worm tubes are concentrated near the movable spines on the opisthosoma, but rare on recessed chilarial or opercular pleurites, the prosoma, and telson. Barnacles are disproportionately concentrated in entapophyseal pits on the opisthosoma and in the longitudinal furrows flanking the cardiac lobe of the prosoma. Bryozoans are concentrated near movable marginal spines of the opisthosoma, but also found on all areas of the prosoma, opisthosoma, and hinge area in between, as well as the telson. Different morphologic sites for their respective modal concentrations may result from competitive exclusion of bryozoans by barnacles. Genal angles have lower statistically predicted frequencies of bryozoans, barnacles, and sand worm tubes. Apertural openings of calcareous tubes are predominantly posteriorly oriented whereas the anterior magin of slipper shells are randomly oriented on the opisthosoma. Eschewing differential mortality, nonrandom distributions indicate possible: rugophilic (groove-seeking) larval settlement behavior for barnacles that preferred the recessed hinge area, longitudinal grooves, and pits; rheophilic (current-seeking) larval settlement behavior for the gastropods and tube-building polychaetes that filter feed in the eddies generated near the movable spines of the downcurrent-sloping opisthosoma; and geotactic (gravity-influenced) larval settlement or post-settlement migration to the vaulted crest (cardiac lobe). Deficiencies of protruding epizoic skeletons on the genal angles and anterior margin of the host may be due to removal by abrasion as the horseshoe crab plowed through sediment or shearing of the epizoans from the carapace substratum in strong currents or waves.     

Modal metasomatism in the Kaapvaal craton lithosphere: constraints on timing and genesis from U–Pb zircon dating of metasomatized peridotites and MARID-type xenoliths

Modal metasomatism in the Kaapvaal craton lithosphere is well documented in upper mantle xenoliths sampled by both group I (mainly late Cretaceous) and group II (mainly early Cretaceous to late Jurassic) kimberlites in the Kimberley area. The metasomatic style is characterized by introduction of K, H and large ion lithophile/high field strength (LIL/HFS) elements into the lithospheric mantle leading to the crystallization of hydrous potassic phases such as phlogopite and/or K-amphibole. Textures indicate that the hydrous phases either replace pre-existing assemblages in peridotites, forming the metasomatized peridotite suite (phlogopite–K-richterite–peridotites: PKPs) or crystallize from K-rich melts, forming the mica–amphibole–rutile–ilmenite–diopside (MARID) suite of xenoliths. These K-rich assemblages become potential low melting source components for alkaline incompatible trace element enriched magmas. The timing of metasomatism and its temporal and possible genetic relation to kimberlite magmatism is poorly constrained because of the rarity of phases in the metasomatic assemblages suitable for precise dating. Here we present precise sensitive high resolution ion microprobe (SHRIMP) U–Pb formation ages of 88 ± 2 (1σ=1 standard deviation) and 82 ± 3 Ma data for zircons from a K-richterite–phlogopite-bearing metasomatized peridotite (PKP) and a MARID xenolith respectively, sampled by a group I kimberlite. Both average PKP and MARID zircon ages are indistinguishable from emplacement ages of group I kimberlites in the Kimberley area dated at 83 ± 4 (2σ) and 84 ± 0.9 Ma. One exceptionally old age spot of 102 ± 5 Ma from a PKP zircon provides evidence for modal metasomatism predating group I kimberlite emplacement by several millions of years with minor resetting of the U–Pb isotopic system of most analyzed PKP zircons to a group I emplacement age. Detailed textural and mineral chemical analysis, including high energy X-ray mapping and analysis of fluid inclusion daughter crystals, indicates a complex reaction history for both PKPs and MARIDs. U–Pb zircon ages from this study combined with literature data and experimentally derived models for MARID formation are used to suggest that MARID-formation is concurrent and genetically related to both group I and II kimberlite magmatism in the Kimberley area. MARID and PKP zircon ages are also consistent with the idea first proposed by Dawson and Smith (Geochim Cosmochim Acta 41: 309–323, 1977) that metasomatized peridotites may form from interaction of hydrous fluids expelled by solidifying MARID-type melts with peridotitic wall rocks. Received: 13 December 1999 / Accepted: 13 April 2000     

Apatite as a monitor of late-stage magmatic processes at Volcán Irazú, Costa Rica

Apatite phenocrysts from the 1963 and 1723 eruptions of Irazú volcano (Costa Rica) record a volatile evolution history that confirms previous melt inclusion studies, and provides additional information concerning the relative and absolute timing of subvolcanic magmatic events. Measurements of H, Cl, and F by secondary ion mass spectrometry reveal multiple populations of apatite in both 1723 and 1963 magmas. Assuming nominal apatite/melt partition coefficients allows us to compare the pattern of melt inclusions and apatites in ternary space, demonstrating the fidelity of the record preserved in apatite, and revealing a complex history of magma mixing with at least two components. The preservation of heterogeneous populations of apatite and of internally heterogeneous crystals requires short timescales (days to years) for these magmatic processes to occur.     

Hydration in solution is critical for stable oxygen isotope fractionation between carbonate ion and water

Various isotope studies require accurate fractionation factors (α’s) between different chemical compounds in thermodynamic equilibrium. Although numerous isotope systems involve aqueous solutions, the conventional theory is formulated for the gas-phase and predicts incorrect α’s for many compounds dissolved in water. Here I show that quantum-chemistry calculations, which take into account solute–water interactions, accurately predict, for instance, oxygen isotope fractionation between dissolved and H₂O (hereafter ). Simple force field and quantum-chemistry calculations for the ‘gas-phase’ ion predict (15‰) at 25 °C. However, based on -clusters with up to 22 H₂O molecules, I calculate a value of 25‰, which agrees with the experimental value of 24.5 ± 0.5‰. Effects of geometry and anharmonicity on the calculated α were also examined. The calculations reveal the critical role of hydration in solution, which is ignored in the gas-phase theory. The approach presented provides an adequate framework for calculating fractionation factors involving dissolved compounds; it may also be used to predict α’s that cannot (or have not yet been) determined experimentally.     

Composition and origin of the Çaldağ oxide nickel laterite,W. Turkey

The Çalda? nickel laterite deposit located in the Aegean region of W. Turkey contains a reserve of 33 million tons of Ni ore with an average grade of 1.14% Ni. The deposit is developed on an ophiolitic serpentinite body which was obducted onto Triassic dolomites in the Late Cretaceous. The deposit weathering profile is both laterally and vertically variable. A limonite zone, which is the main ore horizon, is located at the base of the profile. A hematite horizon is located above the limonite, which in the south of the deposit is capped by Eocene freshwater limestones and in the north by a siliceous horizon. The deposit is unusual in lacking a significant saprolite zone with little development of Ni-silicates. The boundary between the limonite zone and serpentinite below is sharp with a marked decrease in concentrations of MgO from 13 to 1 wt.% over a distance of 2 mm representing the ‘Mg discontinuity’. Ni concentrations within goethite, the main ore mineral, reach a maximum of ~3 wt.% near the base of the limonite zone. Silica concentrations are high throughout most of the laterite with up to 80 wt.% silica in the upper portion of some profiles. The combination of a serpentinite protolith and a high water table at Çalda?, in association with an aggressive weathering environment in a tropical climate, resulted in the formation of an oxide-dominated deposit. The precipitation of silica may coincide with a change in climate with silica precipitation linked to an increase in seasonality. Additional variations within profile morphology are attributed to transportation during and after laterite development as a result of faulting, pocket type laterite formation and slumping, each of which produces a contrasting set of textural and geochemical features.