Titanium- and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps,Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Titanium- and water-rich metamorphic olivine (Fo 86–88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H₂O (up to 0.7 wt%) and TiO₂ contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H₂O (x ~ 0.1 in the formula 4Mg₂SiO₄·(1?x)Mg(OH,F)₂·xTiO₂) than Ti-clinohumite in the sample matrix (x = 0.34–0.46). In addition to TiO₂ and H₂O, secondary olivine contains significant Li (2–60 ppm), B (10–20 ppm), F (10–130 ppm) and Zr (0.9–2.1 ppm). It is enriched in ¹¹B (δ¹¹B = +17 to +23 ‰). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H₂O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.     

Evidence for fullerenes in solid bitumen from pillow lavas of Proterozoic age from Mítov (Bohemian Massif, Czech Republic)

Andesitic pillow lavas containing biogenic, solid bitumen (SB) are a constituent of a Neoproterozoic volcanosedimentary sequence (Teplá-Barrandian unit, Bohemian Massif) in the Mítov area of the Czech Republic. A black shale formation that is crosscut by these andesitic basalts is 565 Ma old. Carbon disulfide extracts of two powdered samples of SB contain 0.2 and 0.3 ppm of C₆₀, respectively, as determined by high-pressure liquid chromatography. The peak assignment based on retention time is fully supported by high-resolution electron ionization mass spectrometry (EI-MS). No C₇₀ was detected, nor was C₆₀ found in two other SB samples from this locality. Other investigated carbonaceous samples from Bohemia (coals and anthracites of Upper Paleozoic age and anthraxolite, graphitoids, and graphite of Upper Proterozoic age) did not contain fullerenes at concentrations above the detection limit of 0.01 ppm. The absence of C₆₀ in these samples was confirmed by EI-MS. The proposed mechanism of fullerene formation involves a primary algal phase, generation of a hydrocarbonaceous mixture in the course of thermal evolution of the sedimentary series, and their high-temperature transformation related to the extrusion of basalt. An important feature for fullerene conservation was the enclosure of fullerenes in SB with a structure similar to glasslike carbon, where the fullerene was protected against oxidation.     

The relation between the heat flow field and the distribution ofP n -wave velocities for the European continent

Summary The dependence of P_n-wave velocities on the heat flow, temperature at the crustmantle boundary and the thickness of the Earth's crust in Europe was investigated in relation to the problem of lateral inhomogeneities in the upper mantle. A map was constructed of the distribution of P_n-wave velocities on the territory of Europe. The relations these investigations yielded, were compared with the results of laboratory experiments and all the results are discussed from the physical point of view. The conclusion drawn is that that temperature and pressure effect provide a sufficient explanation of the observed regional changes of P_n-wave velocities for the European continent.

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auum ¶rt;auu mu n¶rt; ¶rt; nmu uua (P_n) u mn nm, mnam a nmu amuu u m a mumuu n a u¶rt;aa u numa ¶rt;¶rt;m amuu. mumuu n a maa a uu m P_n- a nmu uua. u¶rt;u umam ¶rt;a mama aam u¶rt;au uuu m n¶rt; amuu u u ¶rt;au u mnam mmmm mama n¶rt;aa am. ¶rt;a ¶rt;, m ua uu m P_n- a n mum ¶rt;mam um uuu mnam u ¶rt;au a nmu uua.

     

Meteorological microseisms and stratospheric warmings

Summary The meteorological microseisms recorded at Prague are found to be essentially independent of the occurrence of the major midwinter stratospheric warmings. This finding contributes to studying the downward propagation mechanism of some extraterrestrial influences.     

The intensity of the earth's magnetic field in the past derived from the archaeomagnetic data

a n¶rt;u¶rt; amuu amua uuu anmuaum n a n¶rt;u 8500 m nm um au aam m uuu m naama. ¶rt;u u ¶rt;a ¶rt; u ¶rt; m¶rt; mumu auu nau nuu aau mama [1–3] (Puc. 1.B). nma aau auau (Puc.2) mnaua m m m¶rt;a, ¶rt; au n¶rt; amu u, m n¶rt;u 2- ma m, mmu naa auu nu¶rt; n¶rt;a 1000 m u 350 m, au a aumu, mmm 80%- mmu. am au ¶rt;a u anmu ¶rt; m¶rt; mumu (mum) naa auu u¶rt; ma u ¶rt; m naama[5] (Puc. 3). uma a mam nma aaua naaa auu nu¶rt; n¶rt;a 750 m, 200 m u a — 300 m. (Puc. 4.) nmu u ¶rt;a nma amua an¶rt;u n¶rt;u n u ma m (au) auumu m ¶rt;m m (Puc. 5). aa a m¶rt;m nu naamaum n aam ¶rt;uu mu au, anum¶rt;a m uua nm m¶rt;a.

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Dedicated to Academician Alois Zátopek on His 65th Birthday     

Catabolic and anabolic energy for chemolithoautotrophs in deep-sea hydrothermal systems hosted in different rock types

Active deep-sea hydrothermal vents are hosted by a range of different rock types, including basalt, peridotite, and felsic rocks. The associated hydrothermal fluids exhibit substantial chemical variability, which is largely attributable to compositional differences among the underlying host rocks. Numerical models were used to evaluate the energetics of seven inorganic redox reactions (potential catabolisms of chemolithoautotrophs) and numerous biomolecule synthesis reactions (anabolism) in a representative sampling of these systems, where chemical gradients are established by mixing hydrothermal fluid with seawater. The wide ranging fluid compositions dictate demonstrable differences in Gibbs energies (ΔG_r) of these catabolic and anabolic reactions in three peridotite-hosted, six basalt-hosted, one troctolite-basalt hybrid, and two felsic rock-hosted systems. In peridotite-hosted systems at low to moderate temperatures (<∼45 °C) and high seawater:hydrothermal fluid (SW:HF) mixing ratios (>10), hydrogen oxidation yields the most catabolic energy, but the oxidation of methane, ferrous iron, and sulfide can also be moderately exergonic. At higher temperatures, and consequent SW:HF mixing ratios <10, anaerobic processes dominate the energy landscape; sulfate reduction and methanogenesis are more exergonic than any of the aerobic respiration reactions. By comparison, in the basalt-hosted and felsic rock-hosted systems, sulfide oxidation was the predominant catabolic energy source at all temperatures (and SW:HF ratios) considered. The energetics of catabolism at the troctolite-basalt hybrid system were intermediate to these extremes. Reaction energetics for anabolism in chemolithoautotrophs—represented here by the synthesis of amino acids, nucleotides, fatty acids, saccharides, and amines—were generally most favorable at moderate temperatures (22-32 °C) and corresponding SW:HF mixing ratios (∼15). In peridotite-hosted and the troctolite-basalt hybrid systems, ΔG_r for primary biomass synthesis yielded up to ∼900 J per g dry cell mass. The energetics of anabolism in basalt- and felsic rock-hosted systems were far less favorable. The results suggest that in peridotite-hosted (and troctolite-basalt hybrid) systems, compared with their basalt (and felsic rock) counterparts, microbial catabolic strategies—and consequently variations in microbial phylotypes—may be far more diverse and some biomass synthesis may yield energy rather than imposing a high energetic cost.     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.