Possible implications of modal mineralogy for melting in mantle lherzolites

The melting reaction at the solidus of mantle peridotite is commonly peritectic in nature, with liquid and one or more solid phases produced upon melting. In some situations, one of the phases participating on the reactant side of the reaction is present in low abundance. This article explores the possible effects of the low abundance of a reactant phase on the melting behavior of mantle peridotite.For example, spinel lherzolite begins to melt via the peritectic reaction, clinopyroxene + orthopyroxene + spinel = olivine + liquid in the ∼1- to 2-GPa pressure range. In natural spinel lherzolites, spinel is a modally minor mineral and may be infrequently in contact with both clinopyroxene and orthopyroxene. If these mutual contacts are insufficient to generate an interconnected melt, then significant melting may not occur until a combination of minerals that are modally abundant and in contact begin to melt. This scenario could have implications for the physical process of melting and for the timing of formation of an interconnected melt network and separation of the melt from the residue.To begin to investigate this possibility, the spatial relationships between the constituent minerals in two fertile spinel lherzolites were determined by elemental mapping with the electron microprobe. Olivine, orthopyroxene, and clinopyroxene are of similar size, whereas the spinel was smaller and interstitial. Spinel and clinopyroxene are frequently in contact, but mutual contacts of spinel, clinopyroxene, and orthopyroxene are rare. Because of the changes in modal mineralogy anticipated for these lherzolites with increasing temperature, these mutual contacts will be even less common at the solidus. Therefore, an interconnected, potentially extractable, melt may not occur by the solidus spinel + orthopyroxene + clinopyroxene melting reaction.     

Geochemistry and geochronology of proterozoic tholeiite dykes of east antarctica: evidence for mantle metasomatism

Two episodes of tholeiite dyke emplacement have been identified in Archaean high-grade metamorphics of the Napier Complex in Enderby Land. Middle Proterozoic Amundsen dykes are typical continental tholeiites and most of the chemical variation in individual suites can be explained in terms of different degrees of partial melting and low-pressure crystal fractionation. Group I Amundsen tholeiites were derived from a relatively homogeneous source region 1,190±200 m.y. ago, whereas that of the group II Amundsen tholeiites was chemically and isotopically heterogeneous. Group II dykes have various degrees of enrichment in incompatible elements, and commonly show normalised trace element abundance patterns with negative Nb anomalies. These features imply variable metasomatism of the source region by a volatile-rich fluid phase (rather than a melt of any observed igneous composition) enriched in K, Rb, Ba, Th, and possibly La and Ce.Early Proterozoic (2,350±48 m.y.) tholeiites were emplaced at considerable depths in the crust during the waning stages of granulite-facies metamorphism and include a high-Mg suite of possible komatiitic affinity, ranging in composition from hypersthene-rich tholeiite (norite) to quartz-rich tholeiite. They tend to have higher ratios of highly to moderately incompatible elements (e.g., K/Zr, K/Ce), and larger Nb anomalies (i.e., higher K/Nb) compared with middle Proterozoic tholeiites, suggesting derivation from more enriched source regions. Isotopic data are not compatible with significant crustal contamination, but constrain source metasomatism to a time immediately before emplacement. Metasomatism of the source region of the much younger group I tholeiites may have been contemporaneous with that of the high-Mg suite.     

The Late Precambrian Timna igneous complex, Southern Israel: Evidence for comagmatic-type sanukitoid monzodiorite and alkali granite magma

New data from a geochemical, geochronological and isotopic study of the Late Precambrian Timna igneous complex suggest the formation of alkali granites from a LIL-enriched, mantle derived, sanukitoid-type monzodiorite (a silica oversaturated rock with Mg# >60). These data also provide new insights into the petrology, timing and regional tectonic control of the transition from the calc-alkaline to the alkaline magmatic activity in the northern Arabian-Nubian Shield (ANS) during the Late Precambrian.

The Timna alkali granite was formed by fractional crystallization from the monzodioritic magma in a quasi-stratified magmatic cell which formed 610 Ma ago in the 625 Ma old calc-alkaline, porphyritic granite crust. These monzodiorites are mantle-derived, as demonstrated by their high Mg# (63), Cr (230 ppm), and Ni (120 ppm). They are characterized by initial ⁸⁷Sr/⁸⁶Sr of 0.7034, ε-Nd (610 Ma) = +3.4, and are enriched in K₂O (2.9%), Sr (840 ppm), Ba (1290 ppm) and LREE [(La/Lu)_n= 10–25]. The chemical characteristics and REE patterns of the monzodiorites and andesitic dykes of Timna are very similar to Dokhan andesites from northeastern Egypt and the Archean sanukitoids from Canada. The isotopic, geochemical and geochronologic data all indicate that Timna monzodiorites are comagmatic with the alkali granite. The alkali granite is a typical post-orogenic, borderline A-type granite. It is enriched in potassium (K₂O=4.68–6.64%), has a negative europium anomaly (Eu/Eu^*=0.058–0.38) and ε-Nd (610 Ma) of +3.9. The calc-alkaline granite is a typical I-type granite with a small positive europium anomaly (Eu/Eu^*=1.02–1.16). Its age and the Sr, Nd and Pb isotopic characteristics with ε-Nd (625 Ma) of +5.6 to +5.9 are significantly different from these of the alkali granite and monzodiorites, and indicate little interaction with the monzodiorite during the formation of the alkali granite.

The alkali granites are correlative with the post-collisional extensional granites in Jordan and Egypt while the porphyritic granites can be correlated with the late orogenic types. Crustal thickening associated with orogenic compression resulted in crustal anatexis to form the I-type granitic rocks, whereas crustal thinning associated with extension allowed LIL-enriched mantle melts to rise very near to the surface, where space was available for these to pond and fractionate to alkali granite.     

The origin of faceted garnets in sandstones: dissolution or overgrowth?

Faceted garnets from a wide range of geological ages, environments and locations have been studied in polished grain mounts by a combination of backscattered electron microscopy and elemental mapping using energy-dispersive X-ray analysis. In all cases, the areas apparently showing positive relief on the faceted garnet surfaces are compositionally identical to the adjacent grain cores despite a wide variation in detrital garnet compositions. In one case, zoning within the grain core can be traced into the faceted areas on the grain surface. Thus, faceted areas must be considered to form part of the original detrital grains. Together with previously published studies on experimental garnet etching, thermodynamic conditions for garnet growth, textural relationships between faceted garnets and authigenic and detrital phases, and distribution of faceted garnets in the subsurface, this paper provides conclusive proof that faceted garnet surfaces form as a result of dissolution, not overgrowth.     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ¹⁸O and δ³⁴S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O₂ as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)_aq as an oxidant with varying δ¹⁸O_H2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ³⁴S_SO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O₂) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O₂ varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (ε¹⁸O_SO4-H2O) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured value was then used to estimate the oxygen isotope fractionation effects between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ¹⁸O_SO4 values in the biological and abiotic experiments, it is suggested that δ¹⁸O_SO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)_aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions.     

Early Neoproterozoic granulite facies metamorphism of mafic dykes from the Vestfold Block,east Antarctica

Proterozoic mafic dykes from the southwestern Vestfold Block experienced heterogeneous granulite facies metamorphism, characterized by spotted or fractured garnet‐bearing aggregates in garnet‐absent groundmass. The garnet‐absent groundmass typically preserves an ophitic texture composed of lathy plagioclase, intergranular clinopyroxene and Fe–Ti oxides. Garnet‐bearing domains consist mainly of a metamorphic assemblage of garnet, clinopyroxene, orthopyroxene, hornblende, biotite, plagioclase, K‐feldspar, quartz and Fe–Ti oxides. Chemical compositions and textural relationships suggest that these metamorphic minerals reached local equilibrium in the centre of the garnet‐bearing domains. Pseudosection calculations in the model system NCFMASHTO (Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃) yield P–T estimates of 820–870 °C and 8.4–9.7 kbar. Ion microprobe U–Pb zircon dating reveals that the NW‐ and N‐trending mafic dykes were emplaced at 1764 ± 25 and 1232 ± 12 Ma, respectively, whereas their metamorphic ages cluster between 957 ± 7 and 938 ± 9 Ma. The identification of granulite facies mineral inclusions in metamorphic zircon domains is also consistent with early Neoproterozoic metamorphism. Therefore, the southwestern margin of the Vestfold Block is inferred to have been buried to depths of ~30–35 km beneath the Rayner orogen during the late stage of the late Mesoproterozoic/early Neoproterozoic collision between the Indian craton and east Antarctica (i.e. the Lambert Terrane or the Ruker craton including the Lambert Terrane). The lack of penetrative deformation and intensive fluid–rock interaction in the rigid Vestfold Block prevented the nucleation and growth of garnet and resulted in the heterogeneous granulite facies metamorphism of the mafic dykes.     

Natrolite,part I: Refinement of high-order data,separation of internal and external vibrational amplitudes from displacement parameters

A single crystal of natrolite, Na₂Al₂Si₃O₁₀·2H₂O, was studied by X-ray diffraction methods at room temperature. The intensities were measured with MoKα radiation (λ = 0.7107 Å) in a complete sphere of reflection up to sin θ/λ = 0.903 Å^?1. The structure was refined in the orthorhombic space group Fdd2 with a = 18.2929 (7) Å, b = 18.6407(9) Å, c = 6.5871(6) Å, V = 2246 ų, Z = 8. A refinement of high-order diffraction data yielded reliability factors of R(F) = 0.9%, R _w(F) = 0.8%, GoF = 1.40 for 1856 high-angle reflections (0.7 ?in θ/λ <0.903 Å^?1) and R(F) = 1.0%, R _W(F) = 1.2%, GoF = 3.07 for all 3471 independent reflections in the complete sphere of reflection. The T-O distances as well as the T-O-T angles were found to be strongly influenced by the different bond strengths received by the individual oxygen atoms. The T O distances calculated using Baur's extended valence rule agree on average within 0.003 Å with the observed values. An analysis of the mean square displacement amplitudes allowed a separation of the external and internal vibrational amplitudes along the T-O bonds as well as along the Na O and H₂O-O bond directions and the calculation of force constants. The internal vibrational amplitudes (ΔU) of the T-O vibrations are in the range of 5 to 11 × 10^-4 Ų, that is about one order of magnitude smaller than the mean square displacement amplitudes of the external vibrations. The corresponding force constants are F = 354 to 824 Nm^?1. The values of the force constants of the motion of the Na-ion and the water molecule against the framework oxygen atoms lie in the range between F = 57 and 293 Nm^?1. This is the first instance where displacement amplitudes from a zeolite structure refinement could be apportioned between contributions from internal and external vibrations for individual bonds.     

Stabilization of extracellular polymeric substances (Bacillus subtilis) by adsorption to and coprecipitation with Al forms

Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction results in a decrease in EPS bioaccessibility, it may contribute to stabilization of microbial-derived organic carbon (OC) in soil. Here we examined: (i) the chemical fractionation of EPS produced by a common Gram positive soil bacterial strain (Bacillus subtilis) during reaction with dissolved and colloidal Al species and (ii) the resulting stabilization against desorption and microbial decay by the respective coprecipitation (with dissolved Al) and adsorption (with Al(OH)_3(am)) processes. Coprecipitates and adsorption complexes obtained following EPS-Al reaction as a function of pH and ionic strength were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The stability of adsorbed and coprecipitated EPS against biodegradation was assessed by mineralization experiments for 1100 h. Up to 60% of the initial 100 mg/L EPS-C was adsorbed at the highest initial molar Al:C ratio (1.86), but this still resulted only in a moderate OC mass fraction in the solid phase (17 mg/g Al(OH)_3(am)). In contrast, while coprecipitation by Al was less efficient in removing EPS from solution (maximum values of 33% at molar Al:C ratios of 0.1-0.2), the OC mass fraction in the solid product was substantially larger than that in adsorption complexes. Organic P compounds were preferentially bound during both adsorption and coprecipitation. Data are consistent with strong ligand exchange of EPS phosphoryl groups during adsorption to Al(OH)_3(am), whereas for coprecipitation weaker sorption mechanisms are also involved. X-ray photoelectron analyses indicate an intimate mixing of EPS with Al in the coprecipitates, which is not observed in the case of EPS adsorption complexes. The incubation experiments showed that both processes result in overall stabilization of EPS against microbial decay. Stabilization of adsorbed or coprecipitated EPS increased with increasing molar Al:C ratio and biodegradation was correlated with EPS desorption, implying that detachment of EPS from surface sites is a prerequisite for microbial utilization. Results indicate that the mechanisms transferring EPS into Al-organic associations may significantly affect the composition and stability of biomolecular C, N and P in soils. The observed efficient stabilization of EPS might explain the strong microbial character of organic matter in subsoils.     

Tin mineralization in the Dajing tin–polymetallic deposit, Inner Mongolia, China

Dajing is a large-scale tin–polymetallic deposit that hosts the largest tin mine in North China. It is a hydrothermal vein-type deposit containing Sn, Cu, Pb, Zn, Ag, and minor components Co and In. The deposit consists of more than 690 veins hosted within Upper Permian sedimentary rocks.Three mineralization stages and six ore types are recognized with cassiterite constituting the dominant tin mineral. The SnO₂ content of cassiterite increases in the sequence of mineralization stages shear-deformation→cassiterite–quartz→cassiterite–sulfide (or chalcopyrite–pyrite) stage, while the content of FeO, TiO₂, Nb₂O₅, Ta₂O₅, and In₂O₅ tends to decrease with increases in NiO and Ga₂O₅. It is considered that the negative correlation between SnO₂ and FeO, Nb₂O₅, Ta₂O₅, and In₂O₅ results from elemental substitutions. The early stage cassiterite is much richer in Ta and the later stage cassiterite is much poorer in Ti and Fe than is usual in hydrothermal vein type tin deposits. This is interpreted to indicate that the component of early stage cassiterite reflects a granitic magma source while the composition of later stage cassiterite has a more obvious strata source. The compositional variation of cassiterite corresponds to decreasing crystallization temperatures within each stage and between sequential stages with time. The characteristics of REE in cassiterite from two stages are in accord with that of subvolcanic rocks and the Linxi formation. It suggests that tin transported during the cassiterite–quartz stage may have originated from subvolcanic dikes (e.g., dacite porphyry), while in the cassiterite–sulfide stage, tin may have been derived from wallrock (e.g. siltstone) of the Upper Permian-age Linxi Formation.