Spectral survey of the star-forming region W51 e1/e2 at 3 mm

A spectral survey of the W51 e1/e2 star-forming region at 84–115 GHz has yielded detections of 105 molecules and their isotopic species, from simple diatomic or triatomic molecules, such as CO, CS, HCN, up to complex organic compounds, such as CH₃OCH₃, CH₃COCH₃, and C₂H₅OOCH. Ninety-three lines that are absent from the Lovas list of molecular lines observed from space were detected, and approximately half of these were identified. A significant number of the detectedmolecules are typical for hot cores. These include the neutral molecules CH₃OCHO, C₂H₅OH, CH₃COCH₃ etc., which are currently believed to exist in the gas phase only in hot cores and shock-heated gas. In addition, vibrationally excited SiO, C₄H, HCN, l-C₃H, HCCCN, CH₃CN, CH₃OH, H₂O, and SO₂ lines with upper-level temperatures of several hundred Kelvin were found. Such lines can arise only in hot gas with temperatures of the order of 100 K or higher. Apart from neutral molecules, various molecular ions were also detected. Some of these (N₂H⁺, HCO⁺, HCS⁺) usually exist in molecular clouds with high visual extinctions A _V . At the same time, the CF⁺ ion should be observed in photon-dominated regions with A _V values of about unity or lower. An interesting result is the tentative detection of two molecules that have thus far been observed only in the atmospheres of late-type giant stars—MgCN and NaCN. This suggests that the conditions in the hottest W51 regions (probably, in the vicinities of protostars) are close to those in the atmospheres of giant stars. It would be desirable to search for other lines of these molecules to verify these tentative detections. Analysis of the radial velocities of the detected molecules suggests that the contribution from the e2 core dominates the emission of some O-bearing molecules (CH₃OCHO, CH₃CH₂OH), while the contribution of the e1 core dominates the emission of some N-bearing molecules (e.g., CH₃CH₂CN). Thus, the molecular composition of the e2 core may be closer to the composition of the “Compact Ridge” in OMC-1, while the composition of the e1 core is closer to that for the “Hot Core” in the same cloud.     

Thermal lines of methanol towards bipolar outflows

Observations of 26 regions of low-mass star formation and 17 regions of massive star formation in the 5₋₁-4₀ E, 7₀-6₁ A ⁺, 8₀-7₁ A ⁺, and 2_K-1_K methanol lines at 44.1, 84.5, 95.2 GHz, and 96.7 GHz yielded detections of methanol emission in 11 low-mass and 12 high-mass regions. The strongest lines in the low-mass regions were found towards bipolar outflows driven by Class 0 protostars with luminosities higher than or of the order of 10 L _⊙. These lines usually consist of cores 1–2 km s⁻¹ in width, which are emitted by quiescent gas, and broader wings, emitted by gas accelerated by high-velocity jets. The temperature of the accelerated gas derived from rotational diagrams and statistical equilibrium calculations is roughly 20–50 K. This means that a significant fraction of the accelerated gas cools to such temperatures. The widths of the lines detected in the massive star-forming regions are 2–3 km s⁻¹ or higher. Weak, broad wings were found towards only two sources: L1287 and AFGL5142. For most sources, the statistical-equilibrium calculations yielded gas temperatures of about 20–30 K and densities of about 10⁴–10⁶ cm⁻³, which are typical for warm clouds. However, different transitions emit in regions with different physical conditions located within the main beam of the telescope. Most of the 96.7 GHz emission arises in warm gas with kinetic temperatures of about 30 K, while most of the 95.2 GHz emission may arise in hot regions around Young Stellar Objects and/or be related to the wings of bipolar outflows. Published in Russian in Astronomicheskiĭ Zhurnal, 2007, Vol. 84, No. 1, pp. 48–59. The article was translated by the author.     

Determination of molecular gas properties using methyl cyanide lines

A survey has been made of 27 Galactic star-forming regions in the (CH₃CN) 6_K–5_K, 5_K–4_K, and 8_K–7_K lines of methyl cyanide (CH₃CN) at 110, 92, and 147 GHz. Twenty-five sources were detected at 110 GHz, nineteen at 92 GHz, and three at 147 GHz. The strongest CH₃CN emission arises in hot cores in regions of massive star formation. The abundance of CH₃CN in these objects exceeds 10^?9 as a consequence of grain mantle evaporation. Weaker CH₃CN lines were found in a number of sources. These can arise in either warm (30–50 K), dense (>10⁴ cm^?3) clouds or in hot regions with cooler gas.     

A study of the region of massive star formation L379IRS1 in radio lines of methanol and other molecules

The results of spectral observations of the region of massive star formation L379IRS1 (IRAS18265–1517) are presented. The observations were carried out with the 30-m Pico Veleta radio telescope (Spain) at seven frequencies in the 1-mm, 2-mm, and 3-mm wavelength bands. Lines of 24 molecules were detected, from simple diatomic or triatomic species to complex eight- or nine-atom compounds such as CH₃OCHO or CH₃OCH₃. Rotation diagrams constructed from methanol andmethyl cyanide lines were used to determine the temperature of the quiescent gas in this region, which is about 40–50 K. In addition to this warm gas, there is a hot component that is revealed through high-energy lines of methanol and methyl cyanide, molecular lines arising in hot regions, and the presence of H₂O masers and Class II methanol masers at 6.7 GHz, which are also related to hot gas. One of the hot regions is probably a compact hot core, which is located near the southern submillimeter peak and is related to a group of methanol masers at 6.7 GHz. High-excitation lines at other positions may be associated with other hot cores or hot post-shock gas in the lobes of bipolar outflows. The rotation diagrams can be use to determine the column densities and abundances of methanol (10^?9) and methyl cyanide (about 10^?11) in the quiescent gas. The column densities of A- and E-methanol in L379IRS1 are essentually the same. The column densities of other observedmolecules were calculated assuming that the ratios of the molecular level abundances correspond to a temperature of 40 K. The molecular composition of the quiescent gas is close to that in another region of massive star formation, DR21(OH). The only appreciable difference is that the column density of SO₂ in L379IRS1 is at least a factor of 20 lower than the value in DR21(OH). The SO₂/CS and SO₂/OCS abundance ratios, which can be used as chemical clocks, are lower in L379IRS1 than in DR21(OH), suggesting that L379IRS1 is probably younger than DR21(OH).     

Methanol and other molecular tracers of outflows and dense gas in the molecular cloud G345.01+1.79

The results of SEST millimeter observations of the molecular cloud G345.01+1.79 are presented. Spectra of CH₃OH, SO₂, SiO, HCO⁺, C¹⁸O, C³³S, C³⁴S, HCN, and DCN lines have been obtained. Mapping of the cloud in CH₃OH, SiO, and C³⁴S lines indicates that the maximum integrated intensity in the SiO and C³⁴S lines and in low-excitation CH₃OH transitions coincide with the northern group of methanol masers, while the corresponding maximum for high-excitation CH₃OH transitions coincides with the southern methanol-maser group. The physical parameters are estimated from the quasi-thermal CH₃OH lines under the large-velocity-gradient approximation, and their distribution on the sky derived. The density and temperature are higher toward the southern group of methanol masers than in the northern group. This may indicate that star formation is in an earlier stage of evolution in the northern than toward the southern group. A maser component can be distinguished in 14 (of 71) CH₃OH lines. We have detected for the first time weak, probably maser, emission in the CH₃OH lines at 148.11, 231.28, 165.05, 165.06, and 165.07 GHz. A blue wing is clearly visible in the CH₃OH, SiO, C¹⁸O, and SO₂ lines. The emission in this wing is probably associated with a compact source whose velocity is characteristic of the CH₃OH maser emission in the southern group of masers.     

Thermal emission of methanol and other molecules at millimeter wavelengths

The paper reports the results of a survey of Galactic star-forming regions in the methanol lines 8_?1–7₀ E at 229.8 GHz, 3_?2–4_?1 E at 230.0 GHz, 0₀–1_?1 E at 108.9 GHz, and a series of J ₁–J ₀ E lines near 165 GHz. In addition to the methanol lines, lines of methyl cyanide (CH₃CN), cyanoacetylene (HC₃N), methyl formate (HCOOCH₃), and sulphur dioxide (SO₂) were detected. Analysis of the data indicates that the methanol emission arises in warm (30–50 K) gas.     

A study of three massive star-forming regions in CS lines

We have mapped three star-forming regions (G265.14+1.45, G269.16?1.14, G291.27?0.71) in the CS(3–2) and C³⁴S(2–1) lines using the 15 m SEST telescope (Chile), and analyzed the relative positions of methanol and H₂O masers, IRAS sources, and emission maxima in the CS lines. In most cases, the maser positions are close to those of the IRAS sources. We compared the radial velocities of the maser sources and high-density CS cores, and estimated the CS column densities assuming LTE. The sizes, densities, and masses of the dense core are estimated; the masses obtained in the LTE approximation agree with the virial masses.     

Density profiles in molecular cloud cores associated with high-mass star-forming regions

Radial density profiles for the sample of dense cores associated with high-mass star-forming regions from southern hemisphere have been derived using the data of observations in continuum at 250 GHz. Radial density profiles for the inner regions of 16 cores (at distances ≲0.2−0.8 pc from the center) are close on average to the ρ ∝ r ^−α dependence, where α = 1.6 ± 0.3. In the outer regions density drops steeper. An analysis with various hydrostatic models showed that the modified Bonnor-Ebertmodel, which describes turbulent sphere confined by external pressure, is preferable compared with the logotrope and polytrope models practically in all cases. With a help of the Bonnor-Ebert model, estimates of central density in a core, non-thermal velocity dispersion and core size are obtained. The comparison of central densities with the densities derived earlier from the CS modeling reveals differences in several cases. The reasons of such differences are probably connected with the presence of density inhomogenities on the scales smaller than the telescope beam. In most cases non-thermal velocity dispersions are in agreement with the values obtained from molecular line observations.     

Search for class I methanol maser emission toward several supernova remnants

Observations at 44 GHz in the 7₀−6₁ A ⁺ methanol line have been carried out on the 20-m telescope of the Onsala Space Observatory (Sweden) in the directions of the poorly studied region G27.4–0.2 and of several supernova remnants, at the coordinates of the OH(1720) maser satellite emission, with the aim of searching for Class I methanol maser emission in these sources. The region G27.4–0.2 has beenmapped, and contains maser sources and two supernova remnants with similar coordinates and radial velocities, which may accelerate condensation of the ambient gas-dust medium. This may play a role in enhancing the probability of methanol formation and maser emission. This is the first detection of 44 GHz maser emission in this source, and this maser is among the 10% of the strongest Class I methanol masers, within the uncertainties in the integrated flux (of a total of 198 currently knownmasers). A 27′ × 27′ region around the maser has been mapped at 44 GHz in steps of 1′. The 44-GHz emission forms only within the previously known maser region. Further studies in water lines are needed to estimate the influence of shocks from supernovae. No 44-GHz Class I methanol maser emission was detected at the 3σ level at the coordinates of the OH(1720) satellite emission in six supernova remnants; i.e., the presence of OH(1720) emission is not a sufficient condition for the detection of Class I methanol masers.     

Fluid and gas migration in the North German Basin: fluid inclusion and stable isotope constraints

Fluid inclusions have been studied in minerals infilling fissures (quartz, calcite, fluorite, anhydrite) hosted by Carboniferous and Permian strata from wells in the central and eastern part of the North German Basin in order to decipher the fluid and gas migration related to basin tectonics. The microthermometric data and the results of laser Raman spectroscopy reveal compelling evidence for multiple events of fluid migration. The fluid systems evolved from a H₂O–NaCl±KCl type during early stage of basin subsidence to a H₂O–NaCl–CaCl₂ type during further burial. Locally, fluid inclusions are enriched in K, Cs, Li, B, Rb and other cations indicating intensive fluid–rock interaction of the saline brines with Lower Permian volcanic rocks or sediments. Fluid migration through Carboniferous sediments was often accompanied by the migration of gases. Aqueous fluid inclusions in quartz from fissures in Carboniferous sedimentary rocks are commonly associated with co-genetically trapped CH₄–CO₂ inclusions. P–T conditions estimated, via isochore construction, yield pressure conditions between 620 and 1,650 bar and temperatures between 170 and 300°C during fluid entrapment. The migration of CH₄-rich gases within the Carboniferous rocks can be related to the main stage of basin subsidence and stages of basin uplift. A different situation is recorded in fluid inclusions in fissure minerals hosted by Permian sandstones and carbonates: aqueous fluid inclusions in calcite, quartz, fluorite and anhydrite are always H₂O–NaCl–CaCl₂-rich and show homogenization temperatures between 120 and 180°C. Co-genetically trapped gas inclusions are generally less frequent. When present, they show variable N₂–CH₄ compositions but contain no CO₂. P–T reconstructions indicate low-pressure conditions during fluid entrapment, always below 500 bar. The entrapment of N₂–CH₄ inclusions seems to be related to phases of tectonic uplift during the Upper Cretaceous. A potential source for nitrogen in the inclusions and reservoirs is C_org-rich Carboniferous shales with high nitrogen content. Intensive interaction of brines with Carboniferous or even older shales is proposed from fluid inclusion data (enrichment in Li, Ba, Pb, Zn, Mg) and sulfur isotopic compositions of abundant anhydrite from fissures. The mainly light δ³⁴S values of the fissure anhydrites suggest that sulfate is either derived through oxidation and re-deposition of biogenic sulfur or through mixing of SO₄²⁻-rich formation waters with variable amounts of dissolved biogenic sulfide. An igneous source for nitrogen seems to be unlikely since these rocks have low total nitrogen content and, furthermore, even extremely altered volcanic rocks from the study area do not show a decrease in total nitrogen content.     

Thioarsenides: a case for long-range Lewis acid–base-directed van der Waals interactions

Electron density distributions, bond paths, Laplacian and local-energy density properties have been calculated for a number of As₄S _n (n = 3, 4 and 5) thioarsenide molecular crystals. On the basis of the distributions, the intramolecular As–S and As–As interactions classify as shared bonded interactions, and the intermolecular As–S, As–As and S–S interactions classify as closed-shell van der Waals (vdW) bonded interactions. The bulk of the intermolecular As–S bond paths link regions of locally concentrated electron density (Lewis-base regions) with aligned regions of locally depleted electron density (Lewis-acid regions) on adjacent molecules. The paths are comparable with intermolecular paths reported for several other molecular crystals that link aligned Lewis base and acid regions in a key–lock fashion, interactions that classified as long-range Lewis acid–base-directed vdW interactions. As the bulk of the intermolecular As–S bond paths (~70%) link Lewis acid–base regions on adjacent molecules, it appears that molecules adopt an arrangement that maximizes the number of As–S Lewis acid–base intermolecular bonded interactions. The maximization of the number of Lewis acid–base interactions appears to be connected with the close-packed array adopted by molecules: distorted cubic close-packed arrays are adopted for alacránite, pararealgar, uzonite, realgar and β-AsS and the distorted hexagonal close-packed arrays adopted by α- and β-dimorphite. A growth mechanism is proposed for thioarsenide molecular crystals from aqueous species that maximizes the number of long-range Lewis acid–base vdW As–S bonded interactions with the resulting directed bond paths structuralizing the molecules as a molecular crystal.     

Map of the 6.7 GHz class II methanol maser emission of the protoplanetary disk G23.01-0.41

We present images of the star-forming regionG23.01–0.41 at 6.7GHz in the Class II methanol maser transition 5₁–6₀ A ⁺, produced from archival observations on the European VLBI Network. Our map of the source and its maser spots contains 24 maser components. The data for each spot—absolute coordinates, coordinates relative to the calibration feature, peak flux and flux integrated over the spot, size, position angle, velocity along the line of sight, and line full width at half-maximum—are collected in tabular form. The spatial region occupied by the maser spots is approximated by a 200×130 milliarcsec ellipse in position angle PA = −0.40°, centered on the absolute coordinates α ₀ = 18^h34^m40.282^s, δ ₀ = −09°00′38.27″ (J2000). If the source is a protoplanetary disk, then, for the distance estimate derived from trigonometric parallax, its diameter is 1800 AU, and the mass of the central protostar is 23.5M _⊙.     

Eutectic temperatures and melting relations in the Fe–O–S system at high pressures and temperatures

We have investigated melting relations in the Fe–O–S ternary system in the pressure range of 15–27 GPa and 1873 K. Subsolidus phase relations are Fe, Fe₃S₂, and FeO up to 17 GPa and Fe, Fe₃S, and FeO above this pressure. The eutectic temperature slightly decreases from ambient pressure to 17 GPa, whereas increases above this pressure. The eutectic temperature in this study is 100 K lower than that in the Fe–S binary system. The oxygen content in the Fe–O–S eutectic liquid drops when the coexisting solid phases changes from FeS to Fe₃S₂. The cotectic lines in the ternary phase diagram lie close to the Fe–FeS binary axis. The isothermal sections indicate that oxygen solubility in the Fe–O–S liquid increases with increasing temperature, and with increasing sulfur content. The solubility of sulfur in the solid Fe has a maximum value at the eutectic temperature, and decreases with increasing temperature. Our results could have important implications for formation and composition of the Martian core.     

Parameters of warm molecular clouds from methyl acetylene observations

The results of a survey of 63 Galactic star-forming regions in the 6_K–5_K and 5 _K –4_K methyl acetylene lines at 102.5 and 85.5 GHz are presented. Fourty-three sources were detected at 102.5 GHz, and twenty-five at 85.5 GHz. Emission was detected toward molecular clouds with kinetic temperatures of 20–60 K (so-called “warm clouds”). The CH₃CCH abundances in these clouds are about several ×10^?9. Five sources (NGC 2264, G30.8-0.1, G34.26+0.15, DR 21(OH), S140) were mapped using the maximum-entropy method. The sizes of the mapped clouds fall in the range 0.1–1.7 pc, and the clouds have virial masses of 90–6200 M_⊙ and densities between 6×10⁴ and 6×10⁵ cm^?3. The CH₃CCH sources coincide spatially with the CO and CS sources. Chemical-evolution simulations show that the typical methyl acetylene abundances in the observed clouds correspond to ages of ≈6×10⁴ years.     

The mechanisms of water diffusion in polymerized silicate melts

Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz₂₉Or₇₁, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D _water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz₂₈Ab₃₈ Or₃₄, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, D_water is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H₂O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H₂O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H₂O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H₂O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of D_water versus water content implies that increases with water content. The change from linear to exponential dependence of D_water between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996     

The influence of degradation of the swamp and alpine meadows on CH<Subscript>4</Subscript> and CO<Subscript>2</Subscript> fluxes on the Qinghai-Tibetan Plateau

CH₄ and CO₂ fluxes from a high-cold swamp meadow and an alpine meadow on the Qinghai-Tibetan Plateau, subject to different degrees of degradation, were measured over a 12-month period. Air temperature, soil temperature and moisture, and the depths of the water table and thawing-freezing layer were determined. For swamp meadows, the greater the degradation, the lesser the carbon efflux. CH₄ emissions at the nondegraded swamp meadow site were 1.09–3.5 and 2.5–11.27 times greater, and CO₂ emissions 1.08–1.69 and 1.41–4.43 times greater, respectively, than those from moderately and severely degraded sites. For alpine meadows, the greater the degradation, the greater the CH₄ consumption and CO₂ emissions. CH₄ consumption at the severely degraded alpine meadow site was 6.6–21 and 1.1–5.25 times greater, and CO₂ emissions 1.05–78.5 and 1.04–6.28 times greater, respectively, than those from the nondegraded and moderately degraded sites. The CH₄ and CO₂ fluxes at both sites were significantly correlated (R ² > 0.59, P < 0.05) with air temperature, soil temperature, and topsoil (0–5 cm depth) moisture, indicating these to be the main environmental factors affecting such fluxes.     

Shlykovite KCa[Si4O9(OH)] · 3H2O and cryptophyllite K2Ca[Si4O10] · 5H2O, new mineral species from the Khibiny alkaline pluton, Kola Peninsula, Russia

New minerals, shlykovite and cryptophyllite, hydrous Ca and K phyllosilicates, have been identified in hyperalkaline pegmatite at Mount Rasvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. They are the products of low-temperature hydrothermal activity and are associated with aegirine, potassium feldspar, nepheline, lamprophyllite, eudialyte, lomonosovite, lovozerite, tisinalite, shcherbakovite, shafranovskite, ershovite, and megacyclite. Shlykovite occurs as lamellae up to 0.02 × 0.02 × 0.5 mm in size or fibers up to 0.5 mm in length usually combined in aggregates up to 3 mm in size, crusts, and parallel-columnar veinlets. Cryptophyllite occurs as lamellae up to 0.02 × 0.1 × 0.2 mm in size intergrown with shlykovite being oriented parallel to {001} or chaotically arranged. Separate crystals of the new minerals are transparent and colorless; the aggregates are beige, brownish, light cream, and pale yellowish-grayish. The cleavage is parallel to (001) perfect. The Mohs hardness of shlykovite is 2.5–3. The calculated densities of shlykovite and cryptophyllite are 2.444 and 2.185 g/cm³, respectively. Both minerals are biaxial; shlykovite: 2V _meas = −60(20)°; cryptophyllite: 2V _meas > 70°. The refractive indices are: shlykovite: α = 1.500(3), β = 1.509(2), γ = 1.515(2); cryptophyllite: α = 1.520(2), β = 1.523(2), γ = 1.527(2). The chemical composition of shlykovite determined by an electron microprobe (H₂O determined from total deficiency) is as follows, wt %: 0.68 Na₂O, 11.03 K₂O, 13.70 CaO, 59.86 SiO₂, 14.73 H₂O; the total is 100.00. The empirical formula calculated on the basis of 13 O atoms (OH/H₂O calculated from the charge balance) is (K_0.96Na_0.09)_Σ1.05Ca_1.00Si_4.07O_9.32(OH)_0.68 · 3H₂O. The idealized formula is KCa[Si₄O₉(OH)] · 3H₂O. The chemical composition of cryptophyllite determined by an electron microprobe (H₂O determined from the total deficiency) is as follows, wt %: 1.12 Na₂O, 17.73 K₂O, 11.59 CaO, 0.08 Al₂O₃, 50.24 SiO₂, 19.24 H₂O, the total is 100.00. The empirical formula calculated on the basis of (Si,Al)₄(O,OH)₁₀ (OH/H₂O calculated from the charge balance) is (K_1.80Na_0.17)_Σ1.97Ca_0.99Al_0.01Si_3.99O_9.94(OH)_0.06 · 5.07H₂O. The idealized formula is K₂Ca[Si₄O₁₀] · 5H₂O. The crystal structures of both minerals were solved on single crystals using synchrotron radiation. Shlykovite is monoclinic; the space group is P2₁/n; a = 6.4897(4), b = 6.9969(5), c = 26.714(2)?, β = 94.597(8)°, V = 1209.12(15)?³, Z = 4. Cryptophyllite is monoclinic; the space group is P2₁/n; a = 6.4934(14), b = 6.9919(5), c = 32.087(3)?, β = 94.680(12)°, V= 1451.9(4)?, Z = 4. The strongest lines of the X-ray powder patterns (d, ?-I, [hkl] are: shlykovite 13.33–100[002], 6.67–76[004], 6.47–55[100], 3.469–45[021], 3.068–57[$ \bar 1 $ \bar 1 21], 3.042–45[121], 2.945–62[ 23], 2.912–90[025, 12, 211]; cryptophyllite 16.01–100[002], 7.98–24[004], 6.24–48[101], 3.228–22[$ \bar 1 $ \bar 1 09], 3.197–27[0.0.10], 2.995–47[122], 2.903–84[123, 204, $ \bar 1 $ \bar 1 24, 211], 2.623–20[028, 08, 126]. Shlykovite and cryptophyllite are members of new related structural types. Their structures are based on a two-layer packet consisting of tetrahedral Si layers linked with octahedral Ca chains. Mountainite, shlykovite and cryptophyllite could be combined into the mountainite structural family. Shlykovite is named in memory of Russian geologist V. G. Shlykov (1941–2007); the name cryptophyllite is from the Greek words meaning concealed and leaf that allude to its layered structure (phyllosilicate) in combination with a lamellar habit and intimate intergrowths with visually indistinguishable shlykovite. Type specimens of the minerals are deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

Fluid evolution at the Variscan front in the vicinity of the Aachen thrust

Quartz–carbonate–chlorite veins were studied in borehole samples of the RWTH-1 well in Aachen. Veins formed in Devonian rocks in the footwall of the Aachen thrust during Variscan deformation and associated fluid flow. Primary fluid inclusions indicate subsolvus unmixing of a homogenous H₂O–CO₂–CH₄–(N₂)–Na–(K)–Cl fluid into a H₂O–Na–(K)–Cl solution and a vapour-rich CO₂–(H₂O, CH₄, N₂) fluid. The aqueous end-member composition resembles that of metamorphic fluids of the Variscan front zone with salinities ranging from 4 to 7% NaCl equiv. and maximum homogenisation temperatures of close to 400°C. Pressure estimates indicate a burial depth between 4,500 and 8,000 m at geothermal gradients between 50 and 75°C/26 MPa, but pressure decrease to sublithostatic conditions is also indicated, probably as a consequence of fracture opening during episodic seismic activity. A second fluid system, mainly preserved in pseudo-secondary and secondary fluid inclusions, is characterised by fluid temperatures between 200 and 250°C and salinities of <5% NaCl equiv. Bulk stable isotope analyses of fluids released from vein quartz, calcite, and dolomite by decrepitation yielded δD_H2O values from −89 to −113 ‰, δ¹³C_CH4 from −26.9 to −28.9‰ (VPDB) and δ¹³C_CO2 from −12.8 to −23.3‰ (VPDB). The low δD and δ¹³C range of the fluids is considered to be due to interaction with cracked hydrocarbons. The second fluid influx caused partial isotope exchange and disequilibrium. It is envisaged that an initial short lived flux of hot metamorphic fluids expelled from the epizonal metamorphic domains of the Stavelot–Venn massif. The metamorphic fluid was focused along major thrust faults of the Variscan front zone such as the Aachen thrust. A second fluid influx was introduced from formation waters in the footwall of the Aachen thrust as a consequence of progressive deformation. Mixing of the cooler and lower salinity formation water with the hot metamorphic fluid during episodic fluid trapping resulted in an evolving range of physicochemical fluid inclusion characteristics.     

Surface stabilization of organics on hematite by conversion from terminal to bridging adsorption structures

Insight into the complexation of organic molecules on hematite surfaces was obtained from molecular-level studies of a simple probe molecule (methanol) with the R-cut surface of hematite. The R-cut crystal orientation of hematite, designated in this paper as α-Fe₂O₃(012), has two stable surface structures under ultrahigh vacuum (UHV) conditions based on low-energy electron diffraction (LEED) measurements. These are a (1×1) structure consisting of a bulk terminated arrangement of undercoordinated Fe³⁺ and O²⁻ surface sites and a (2×1) reconstructed structure with unknown atomic structure. Whereas the (1×1) surface is essentially free of Fe²⁺, the (2×1) surface possesses a high surface concentration of Fe²⁺ sites based on electronic structure measurements using electron energy loss spectroscopy (EELS). Methanol adsorbs dissociatively on the (1×1) surface by coordination of the molecule’s oxygen atom at a Fe³⁺ site followed by transfer of the alcohol proton to a bridging O²⁻ surface site, resulting in terminal OCH₃ and bridging OH groups. Most of the dissociated methanol molecules recombine during heating and desorb in vacuum as methanol at 365 and 415 K for the (1×1) and (2×1) surfaces, respectively. However, a significant amount of the terminal OCH₃ and bridging OH groups interchange as the surface is heated above room temperature (RT), resulting in bridging OCH₃ and terminal OH groups. The bridging OCH₃ groups are retained on the surface to higher temperature than the terminal OCH₃ groups, but eventually decompose at about 550 K via a disproportionation reaction that forms gaseous CH₃OH and H₂CO. As a result of the disproportionation reaction, some surface Fe³⁺ sites are reduced to Fe²⁺ sites. The exchange process competes more successfully with recombinative desorption of methanol (from reaction of terminal OCH₃ and bridging OH groups) on the (2×1) surface, despite the fact that this surface is already partially reduced, because terminal OCH₃ groups are more stable on this surface than on the (1×1) surface. Based on these molecular-level findings, extensive exchange terminal organic ligands and bridging OH groups may play a significant role in stabilizing organics on hematite mineral surfaces. Such exchange processes may also play a role in destabilizing hematite surfaces toward reductive dissolution.     

OH in zoned amphiboles of eclogite from the western Tianshan,NW-China

Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member ( ^B Na₂ ^C M²⁺ ₃ M³⁺ ₂ ^T Si₈(OH)₂) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition ( ^A _0.5 ^B Ca_1.5Na_0.5 ^C M ²⁺ _4.5 M _0.5^{3+ T} Si_7.5Al_0.5(OH)₂) (A = Na and/or K; M ²⁺ = Mg and Fe²⁺; M ³⁺ = Fe³⁺ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm⁻¹) which can be attributed to a local O(3)-H dipole surrounded by ^{M(1) M(3)}Mg₃, ^{M(1) M(3)}Mg₂Fe²⁺ and ^{M(1) M(3)} Fe²⁺ ₃, respectively, an empty A site and ^T Si₈ environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm⁻¹) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism.