Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

Metamorphic history of the Jutogh Series in the Simla klippe,lower Himalayas

The metamorphic rocks of the Jutogh Series around Simla, structurally overlying the less metamorphosed rock groups along a thrust contact, have been involved in three phases of deformation and two episodes of metamorphism. The first metamorphism is in the albite-epidote-amphibolite facies in a major part of the area, reaching the amphibolite facies locally in the central part. This metamorphism is late-to post-kinematic with reference to the F ₁ movement, the thermal peak having been reached in a post-F ₁ pre-F ₂ static phase. The second metamorphism, syn-to post-tectonic with respect to F ₂ but preceding F ₃, is generally in the greenschist facies, and only locally in the albite-epidote-amphibolite facies in the higher structural levels. Metamorphic overprinting has caused widespread retrogression and disequilibrium assemblages. As the large scale recumbent folding and thrusting of F ₁ and F ₂ phases belong to the Tertiary Himalayan orogeny, the metamorphism in the Jutogh Series could not have been Precambrian in age.     

Humic acids: Their detergent qualities and potential uses in pollution remediation

Humic acids are amphiphilic species whose behavior in aqueous solution suggests that they form pseudomicelles–aggregates akin to the micelles familiar from synthetic surfactant chemistry. It is thought that humic pseudomicelles can be formed by both intramolecular coiling and intermolecular association, depending on the molecular weight, structural characteristics, and polydispersity of the humic acid in question. The process does not feature a critical micelle concentration. Experimental evidence indicates that metal ions enhance the detergent character of dissolved humic acid by facilitating the coiling and folding of the polymer chains. A recently conceived alternative model suggests that humic acids consist of relatively small subunits that associate through weak molecular interactions. This view appears to run counter to certain experimental observations, but deserves careful attention. The strong association between metal ions and solid humic acid makes it possible to use an inexpensive commercial grade for the decontamination of polluted water. A continuous elution process through a column packed with humic acid allows for the removal of both heavy metals and organic xenobiotics from aqueous solution.     

Geochemistry of high-grade eclogites and metarodingites from the Central Alps

Analyses for major, minor, and trace element contents of metamorphosed, variably rodingitized mafic rocks demonstrate substantial removal of Na and as much as three-fold gains in Ca as a consequence of rodingitization. Modest declines in Si and Fe can be explained in terms of dilution effects. Losses in K and Ba do not correlate with Ca% and may have been caused by an alteration process not related to the rodingitization. The Ca-metasomatism was not accompanied by a gain in Sr. The relative contents of Ti, Zr, Hf, Y, Co, Sc, and heavy REE show no readily detectable changes, despite the rodingitization (±other alteration) and subsequent metamorphisms, namely, eclogite facies (T800° C, P 20kbar) followed by amphibolite facies, sillimanite zone. Protoliths were tholeiitic basalt or diabase, and gabbro, with trace element contents indicative of a spreading center origin. Trace element and REE patterns indicate low-pressure fractionation of this magma, with plagioclase stable. This petrogenesis is consistent with prior conclusions on the shallow crustal origin of the protolith of the eclogite-metarodingite-garnet lherzolite suite in the Cima Lunga-Adula nappe, Central Alps. Based on their bulk chemical composition, the mafic rocks in this suite could be the equivalent of Mesozoic ophiolitic rocks in the more external parts of the Alps.     

The Okavango giant mafic dyke swarm (NE Botswana): its structural significance within the Karoo Large Igneous Province

The structural organization of a giant mafic dyke swarm, the Okavango complex, in the northern Karoo Large Igneous Province (LIP) of NE Botswana is detailed. This N110°E-oriented dyke swarm extends for 1500 km with a maximum width of 100 km through Archaean basement terranes and Permo-Jurassic sedimentary sequences. The cornerstone of the study is the quantitative analysis of N>170 (exposed) and N>420 (detected by ground magnetics) dykes evidenced on a ca. 80-km-long section lying in crystalline host-rocks, at high-angle to the densest zone of the swarm (Shashe area). Individual dykes are generally sub-vertical and parallel to the entire swarm. Statistical analysis of width data indicates anomalous dyke frequency (few data <5.0 m) and mean dyke thickness (high value of 17 m) with respect to values classically obtained from other giant swarms. Variations of mean dyke thicknesses from 17 (N110°E swarm) to 27 m (adjoining and coeval N70°E giant swarm) are assigned to the conditions hosting fracture networks dilated as either shear or pure extensional structures, respectively, in response to an inferred NNW–SSE extension. Both fracture patterns are regarded as inherited brittle basement fabrics associated with a previous (Proterozoic) dyking event. The Okavango N110°E dyke swarm is thus a polyphase intrusive system in which total dilation caused by Karoo dykes (estimated frequency of 87%) is 12.2% (6315 m of cumulative dyke width) throughout the 52-km-long projected Shashe section. Assuming that Karoo mafic dyke swarms in NE Botswana follow inherited Proterozoic fractures, as similarly applied for most of the nearly synchronous giant dyke complexes converging towards the Nuanetsi area, leads us to consider that the resulting triple junction-like dyke/fracture pattern is not a definitive proof for a deep mantle plume in the Karoo LIP.     

Depth of the base of the Jackson aquifer, based on geophysical exploration, southern Jackson Hole, Wyoming, USA

 A geophysical survey was conducted to determine the depth of the base of the water-table aquifer in the southern part of Jackson Hole, Wyoming, USA. Audio-magnetotellurics (AMT) measurements at 77 sites in the study area yielded electrical-resistivity logs of the subsurface, and these were used to infer lithologic changes with depth. A 100–600 ohm-m geoelectric layer, designated the Jackson aquifer, was used to represent surficial saturated, unconsolidated deposits of Quaternary age. The median depth of the base of the Jackson aquifer is estimated to be 200 ft (61 m), based on 62 sites that had sufficient resistivity data. AMT-measured values were kriged to predict the depth to the base of the aquifer throughout the southern part of Jackson Hole. Contour maps of the kriging predictions indicate that the depth of the base of the Jackson aquifer is shallow in the central part of the study area near the East and West Gros Ventre Buttes, deeper in the west near the Teton fault system, and shallow at the southern edge of Jackson Hole. Predicted, contoured depths range from 100 ft (30 m) in the south, near the confluences of Spring Creek and Flat Creek with the Snake River, to 700 ft (210 m) in the west, near the town of Wilson, Wyoming. Received, May 1997 · Revised, February 1998 · Accepted, April 1998     

Micro- and nano-textural evidence of Ti(–Ca–Fe) mobility during fluid–rock interactions in carbonaceous lawsonite-bearing rocks from New Zealand

Understanding the mobility of chemical elements during fluid–rock interactions is critical to assess the geochemical evolution of a rock undergoing burial and metamorphism and, more generally, to constrain the geochemical budget of the subduction factory. In particular, determining the behavior and mobility of Ti in aqueous fluids constitutes a great challenge that is still under scrutiny. Here, we study plant fossils preserved in blueschist metasedimentary rocks from the Marybank Formation (New Zealand). Using scanning and transmission electron microscopies (SEM and TEM), we show that the carbonaceous material (CM) composing the fossils contains abundant nano-inclusions of Ti- and Fe-oxides. These nanocrystals are mainly anatase, rutile, and Fe–Ti oxides. The mineral composition observed within the fossils is significantly different from that detected in the surrounding rock matrix. We propose that Ti and Fe might have been mobilized by the alteration of a detrital Ti–Fe-rich protolith during an early diagenetic event under acidic and reducing conditions. Aqueous fluids rich in organic ligands released by the degradation of organic matter may have been involved. Moreover, using mass balance and petrological observations, we show that the contrasted mineralogy between the rock matrix and the fossil CM might be the consequence of the chemical isolation of fossil CM during the prograde path of the rock. Such an isolation results from the early formation of quartz and Fe-rich phyllosilicate layers enclosing the fossil as characterized by SEM and TEM investigations. Overall, this study shows that investigating minerals associated with CM down to the nanometer scale in metamorphic rocks can provide a precious record of early prograde geochemical conditions.     

Core formation and the oxidation state of the Earth: Additional constraints from Nb, V and Cr partitioning

We have combined metal-silicate partitioning data from the literature with new experimental results at 1.5-8 GPa and 1480-2000 °C to parameterize the effects of pressure, temperature and composition on the partitioning of V, Cr and Nb between liquid Fe metal (with low S and C content) and silicate melt.Using information from the steelmaking literature to correct for interactions in the metal phase, we find that, for peridotitic silicate melts, metal-silicate partition coefficients are given by:

     

Biotite weathering and nutrient uptake by ectomycorrhizal fungus, Suillus tomentosus, in liquid-culture experiments

Ectomycorrhiza-forming fungi (EMF) alter the nutrient-acquisition capabilities of vascular plants, and may play an important role in mineral weathering and the partitioning of products of weathering in soils under nutrient-limited conditions. In this study, we isolated the weathering function of Suillus tomentosus in liquid-cultures with biotite micas incubated at room temperature. We hypothesized that the fungus would accelerate weathering by hyphal attachment to biotite surfaces and transmission of nutrient cations via direct exchange into the fungal biomass. We combined a mass-balance approach with scanning electron microscopy (SEM) and atomic force microscopy (AFM) to estimate weathering rates and study dissolution features on biotite surfaces. Weathering of biotite flakes was about 2-3 orders of magnitude faster in shaken liquid-cultures with fungus compared to shaken controls without fungus, but with added inorganic acids. Adding fungus in nonshaken cultures caused a higher dissolution rate than in inorganic pH controls without fungus, but it was not significantly faster than organic pH controls without fungus. The K⁺, Mg²⁺ and Fe²⁺ from biotite were preferentially partitioned into fungal biomass in the shaken cultures, while in the nonshaken cultures, K⁺ and Mg²⁺ was lost from biomass and Fe²⁺ bioaccumulated much less. Fungal hyphae attached to biotite surfaces, but no significant surface changes were detected by SEM. When cultures were shaken, the AFM images of basal planes appeared to be rougher and had abundant dissolution channels, but such channel development was minor in nonshaken conditions. Even under shaken conditions the channels only accounted for only 1/100 of the total dissolution rate of 2.7 × 10⁻¹⁰ mol of biotite m⁻² s⁻¹. The results suggest that fungal weathering predominantly occurred not by attachment and direct transfer of nutrients via hyphae, but because of the acidification of the bulk liquid by organic acids, fungal respiration (CO₂), and complexation of cations which accelerated dissolution of biotite. Results further suggest that both carbohydrate source (abundant here) and a host with which nutrients are exchanged (missing here) may be required for EMF to exert an important weathering effect in soils. Unsaturated conditions and physical dispersal of nutrient-rich minerals in soils may also confer a benefit for hyphal growth and attachment, and promote the attachment-mediated weathering which has been observed elsewhere on soil mineral surfaces.     

Age and geochemistry of the Newania dolomite carbonatites, India: implications for the source of primary carbonatite magma

The Newania carbonatite complex of India is one of the few dolomite-dominated carbonatites of the world. Intruding into Archean basement gneisses, the rocks of the complex have undergone limited diversification and are not associated with any alkaline silicate rock. Although the magmatic nature of the complex was generally accepted, its age of emplacement had remained equivocal because of the disturbed nature of radioisotope systems. Many questions about the nature of its mantle source and mode of origin had remained unanswered because of lack of geochemical and isotopic data. Here, we present results of our effort to date the complex using ¹⁴⁷Sm–¹⁴³Nd, ²⁰⁷Pb–²⁰⁶Pb and ⁴⁰Ar–³⁹Ar dating techniques. We also present mineral chemistry, major and trace element geochemistry and Sr–Nd isotopic ratio data for these carbonatites. Our age data reveal that the complex was emplaced at ~1,473 Ma and parts of it were affected by a thermal event at ~904 Ma. The older ²⁰⁷Pb–²⁰⁶Pb ages reported here (~2.4 Ga) and by one earlier study (~2.3 Ga; Schleicher et al. Chem Geol 140:261–273, 1997) are deemed to be a result of heterogeneous incorporation of crustal Pb during the post-emplacement thermal event. The thermal event had little effect on many magmatic signatures of these rocks, such as its dolomite–magnesite–ankerite–Cr-rich magnetite–magnesio-arfvedsonite–pyrochlore assemblage, mantle like δ¹³C and δ¹⁸O and typical carbonatitic trace element patterns. Newania carbonatites show fractional crystallization trend from high-Mg to high-Fe through high-Ca compositions. The least fractionated dolomite carbonatites of the complex possess very high Mg# (≥80) and have similar major element oxide contents as that of primary carbonatite melts experimentally produced from peridotitic sources. In addition, lower rare earth element (and higher Sr) contents than a typical calcio-carbonatite and mantle like Nb/Ta ratios indicate that the primary magma for the complex was a magnesio-carbonatite melt and that it was derived from a carbonate bearing mantle. The Sr–Nd isotopic data suggest that the primary magma originated from a metasomatized lithospheric mantle. Trace element modelling confirms such an inference and suggests that the source was a phlogopite bearing mantle, located within the garnet stability zone.