Vanadium in peridotites as a proxy for paleo-fO2 during partial melting : prospects, limitations, and implications

The compatibility of vanadium (V) during mantle melting is a function of oxygen fugacity (fO₂): at high fO₂’s, V becomes more incompatible. The prospects and limitations of using the V content of peridotites as a proxy for paleo-fO₂ at the time of melt extraction were investigated here by assessing the uncertainties in V measurements and the sensitivity of V as a function of degree of melt extracted and fO₂. V-MgO and V-Al₂O₃ systematics were found to be sensitive to fO₂ variations, but consideration of the uncertainties in measurements and model parameters indicates that V is sensitive only to relative fO₂ differences greater than ∼2 log units. Post-Archean oceanic mantle peridotites, as represented by abyssal peridotites and obducted massif peridotites, have V-MgO and -Al₂O₃ systematics that can be modeled by 1.5 GPa melting between FMQ − 3 and FMQ − 1. This is consistent with fO₂’s of the mantle source for mid-ocean ridge basalts (MORBs) as determined by the Fe³⁺ activity of peridotitic minerals and basaltic glasses. Some arc-related peridotites have slightly lower V for a given degree of melting than oceanic mantle peridotites, and can be modeled by 1.5 GPa melting at fO₂’s as high as FMQ. However, the majority of arc-related peridotites have V-MgO systematics overlapping that of oceanic mantle peridotites, suggesting that although some arc mantle may melt under slightly oxidizing conditions, most arc mantle does not. The fact that thermobarometrically determined fO₂’s in arc peridotites and lavas can be significantly higher than that inferred from V systematics, suggests that V retains a record of the fO₂ during partial melting, whereas the activity of Fe³⁺ in arc peridotitic minerals and lavas reflect subsequent metasomatic overprints and magmatic differentiation/emplacement processes, respectively.Peridotites associated with middle to late Archean cratonic mantle are characterized by highly variable V-MgO systematics. Tanzanian cratonic peridotites have V systematics indistinguishable from post-Archean oceanic mantle and can be modeled by 3 GPa partial melting at ∼FMQ − 3. In contrast, many South African and Siberian cratonic peridotites have much lower V contents for a given degree of melting, suggesting at first glance that partial melting occurred at high fO₂’s. More likely, however, their unusually low V contents for a given degree of melting may be artifacts of excess orthopyroxene, a feature that pervades many South African and Siberian peridotites but not the Tanzanian peridotites. This is indicated by the fact that the V contents of South African and Siberian peridotites are correlated with increases in SiO₂ content, generating data arrays that cannot be modeled by partial melting but can instead be generated by the addition of orthopyroxene through processes unrelated to primary melt depletion. Correction for orthopyroxene addition suggests that the South African and Siberian peridotites have V-MgO systematics similar to those of Tanzanian peridotites. Thus, if the Tanzanian peridotites represent the original partial melting residues, and if the South African and Siberian peridotites have been modified by orthopyroxene addition, then there is no indication that Archean cratonic mantle formed under fO₂’s significantly greater than that of modern oceanic mantle. Instead, the fO₂’s inferred from the V systematics in these three cratonic peridotite suites are within range of modern oceanic mantle. This also suggests that the transition from a highly reducing mantle in equilibrium with a metallic core to the present oxidized state must have occurred by late Archean times.     

Computational study of tetrahedral Al–Si and octahedral Al–Mg ordering in phengite

 As part of a wider study of the nature and origins of cation order–disorder in micas, a variety of computational techniques have been used to investigate the nature of tetrahedral and octahedral ordering in phengite, K₂ ^[6](Al₃Mg)^[4](Si₇Al)O₂₀(OH)₄. Values of the atomic exchange interaction parameters J _n used to model the energies of order–disorder were calculated. Both tetrahedral Al–Si and octahedral Al–Mg ordering were studied and hence three types of interaction parameter were necessary: for T–T, O–O and T–O interactions (where T denotes tetrahedral sites and O denotes octahedral sites). Values for the T–T and O–O interactions were taken from results on other systems, whilst we calculated new values for the T–O interactions. We have demonstrated that modelling the octahedral and tetrahedral sheets alone and independently produces different results from modelling a whole T–O–T layer, hence justifying the inclusion of the T–O interactions. Simulations of a whole T–O–T layer of phengite indicated the presence of short-range order, but no long-range order was observed. Received: 8 August 2002 / Accepted: 14 February 2003 Acknowledgements The authors are grateful to EPSRC (EJP) and the Royal Society (CIS) for financial support. Monte Carlo simulations were performed on the Mineral Physics Group's Beowulf cluster and the University of Cambridge's High Performance Computing Facility.     

Transport of dissolved methoxy-nonafluorobutane through a saturated column

Solute transport experiments were conducted in a one-dimensional saturated column using dissolved methoxy-nonafluorobutane (HFE-7100), a Novec engineered fluid developed by the 3M Corporation, as the solute. Novec engineered fluids are considered dense non-aqueous phase liquids (DNAPLs) because they are immiscible with water and have a specific gravity greater than one. The HFE-7100 fluid is safer and environmentally friendlier than common DNAPL contaminants such as tetrachloroethylene (PCE) or trichloroethylene (TCE); thus, it is an ideal substitute DNAPL for laboratory groundwater contamination research. Three sets of solute transport experiments were conducted. The first set of experiments was conducted in a glass-bead-packed column using dissolved HFE-7100 as the solute. The second set of experiments was conducted in a sand-packed column using dissolved HFE-7100 as the solute. The third set of experiments was conducted in a sand-packed column using dissolved PCE as the solute. The dissolved HFE-7100 column breakthrough concentrations were compared with dissolved PCE breakthrough concentrations. Results show that the one-dimensional solute transport equation was successful in describing the transport behavior of dissolved HFE-7100. This study demonstrates that the HFE-7100 fluid can be used as a safer substitute DNAPL for groundwater contaminant dissolution and transport research.     

Determination and application of the weights for landslide susceptibility mapping using an artificial neural network

The purpose of this study is the development, application, and assessment of probability and artificial neural network methods for assessing landslide susceptibility in a chosen study area. As the basic analysis tool, a Geographic Information System (GIS) was used for spatial data management and manipulation. Landslide locations and landslide-related factors such as slope, curvature, soil texture, soil drainage, effective thickness, wood type, and wood diameter were used for analyzing landslide susceptibility. A probability method was used for calculating the rating of the relative importance of each factor class to landslide occurrence. For calculating the weight of the relative importance of each factor to landslide occurrence, an artificial neural network method was developed. Using these methods, the landslide susceptibility index (LSI) was calculated using the rating and weight, and a landslide susceptibility map was produced using the index. The results of the landslide susceptibility analysis, with and without weights, were confirmed from comparison with the landslide location data. The comparison result with weighting was better than the results without weighting. The calculated weight and rating can be used to landslide susceptibility mapping.     

Barite deposition resulting from phototrophic sulfide-oxidizing bacterial activity

Barite (BaSO₄) deposits generally arise from mixing of soluble barium-containing fluids with sulfate-rich fluids. While the role of biological processes in modulating barium solubility has been shown, no studies have shown that the biological oxidation of sulfide to sulfate leads to barite deposition. Here we present an example of microbially mediated barite deposition in a continental setting. A spring in the Anadarko Basin of southwestern Oklahoma produces water containing abundant barium and sulfide. As emergent water travels down a stream to a nearby creek, sulfate concentration increases from 0.06 mM to 2.2 mM while Ba²⁺ concentration drops from 0.4 mM to less than 7 μM. Stable isotope analysis, microbial activity studies, and in situ experiments provide evidence that as sulfide-rich water flows down the stream, anaerobic, anoxygenic, phototrophic bacteria play a dominant role in oxidizing sulfide to sulfate. Sulfate then precipitates with Ba²⁺ producing barite as travertine, cements, crusts, and accumulations on microbial mats. Our studies suggest that phototrophic sulfide oxidation and concomitant sulfur cycling could prove to be important processes regulating the cycling of barium in continental sulfur-containing systems.     

The reflection of plane waves in a poroelastic half-space saturated with inviscid fluid

This paper discusses surface displacements, surface strain, rocking, and energy partitioning during reflection-of-plane waves in a fluid-saturated poroelastic half-space. The medium is modeled by Biot's theory, and is assumed to be saturated with inviscid fluid. A linear porosity-modulus relation based on experimental data on sandstones is used to determine the material parameters for Biot's model. Numerical results in terms of angle of incident waves and Poisson's ratio are illustrated for various porosities and degrees of solid frame stiffness. The results show that the amount of solid frame stiffness controls the response of a fluid-saturated porous system. A poroelastic medium with essentially dry-frame stiffness behaves like an elastic medium, and the influence of pore fluid increases as dry-frame stiffness is reduced. The effects of a second P-wave become noticeable in poroelastic media with low dry-frame stiffness.     

Use of time series analysis for the identification of tidal effect on groundwater in the coastal area of Kimje, Korea

The purpose of this study is to apply time series analysis to investigate whether the groundwater quality in the coastal area is affected by the tide. Continuous and regular in situ monitoring data of electrical conductivity (EC) and groundwater level, and tidal level data measured by the National Oceanographic Research Institute were used for the time series analysis. Through the time series analysis, it is known that EC and groundwater level conspicuously fluctuate with two periodicities (15.4 and 0.52-day), which is very similar to those of the tide. Also the behaviors of their fluctuations vary in accordance with the tidal period. These indicate that the groundwater quality has been mainly controlled by the tidal level, and the strength of tidal effect on the groundwater quality is different according to the tidal period.     

Accurate measurement of silver isotopic compositions in geological materials including low Pd/Ag meteorites

Very precise silver (Ag) isotopic compositions have been determined for a number of terrestrial rocks, and high and low Pd/Ag meteorites by utilizing multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The meteorites include primitive chondrites, the Group IAB iron meteorites Canyon Diablo and Toluca, and the Group IIIAB iron meteorite Grant. Silver isotopic measurements are primarily of interest because ¹⁰⁷Ag was produced by decay of the short-lived radionuclide ¹⁰⁷Pd during the formation of the solar system and hence the Pd-Ag chronometer has set constraints on the timing of early planetesimal formation. A 2σ precision of ±0.05‰ can be obtained for analyses of standard solutions when Ag isotopic ratios are normalized to Pd, to correct for instrumental mass discrimination, and to bracketing standards. Caution must be exercised when making Ag isotopic measurements because isotopic artifacts can be generated in the laboratory and during mass spectrometry. The external reproducibility for geological samples based on replicate analyses of rocks is ±0.2‰ (2σ).All chondrites analyzed have similar Ag isotopic compositions that do not differ significantly (>0.3‰) from the ‘terrestrial’ value of the NIST SRM 978a Ag isotope standard. Hence, they show no evidence of excess ¹⁰⁷Ag derived from ¹⁰⁷Pd decay or, of stable Ag isotope fractionation associated with volatile element depletion within the accretion disk or from parent body metamorphism. The Group IAB iron meteorite samples analyzed show evidence of complex behavior and disturbance of Ag isotope systematics. Therefore, care must be taken when using this group of iron meteorites to obtain chronological information based on the Pd-Ag decay scheme.     

Hydrologic modelling of the effect of snowmelt and temperature on a mountainous watershed

Snowmelt-runoff modelling in a mountainous basin is perceived as difficult due to the complexity of simulation. Theoretically, the snowmelt process should be influenced by temperature changes. It is still controversial as how to incorporate the temperature changes into the snowmelt-runoff model in a mountainous basin. This paper presents the results of a study in the North Fork American River basin where the snowmelt-runoff mechanism is modelled by relating the temperature changes to the elevation band in the basin. In this study, a distributed hydrologic model is used to explore the orographic effects on the snowmelt-runoff using the snowfall-snowmelt routine in Soil and Water Assessment Tool (SWAT). Three parameters, namely maximum snowmelt factor, minimum snowmelt factor, and snowpack temperature lag were analysed during the simulation. The model was validated using streamflow data from October 1, 1991 to September 30, 1994 with and without considering the elevation band. The result of this study suggests that the snowmelt-runoff model associated with the elevation band better represents the snowmelt-runoff mechanism in terms of Nash–Sutcliffe coefficient (E _NS ), R ², and Root Mean Square Error (RMSE).