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1.
Seventy-eight molecules have been detected as a result of a spectral survey of the star-forming region DR21(OH) at 84–115 GHz. The abundances of most molecules are typical of those in the dense cores of molecular clouds. The rotational temperatures derived using the lines of most molecules fall in the range 9–56 K, which is also typical for dense cores. However, emission from high-lying levels of methanol and sulfur dioxide was detected; since the rotational temperatures for methanol and sulfur dioxide are 252 and 186 K, this indicates the presence of hot regions. Another fact indicating the existence of hot regions is the detection of CH3OCHO, CH3CH2OH, and CH3OCH3, which have thus far been observed only in hot cores and shock-heated regions. An interesting result is the tentative detection of the J = 2 − 1, v = 1 SiO line, with the upper level energy of 1775 K. This is probably a maser line, similar to but weaker than the well-known SiO masers in the star-forming regions Orion-KL,W51(N), and Sgr B2(N).  相似文献   

2.
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.  相似文献   

3.
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).  相似文献   

4.
Titanium complexation in hydrothermal systems   总被引：3，自引：0，他引：3  
The solubility of rutile in aqueous solutions of HCl, HF, H2SO4, NaOH, and NaF was determined at 500°C, 1000 bar, and hydrogen fugacity from 8 × 10−12 to 10.3 bar (Mn3O4/Mn2O3 and Ni/NiO buffers, dissolution of an Al batch weight). The experimentally determined solubility values were used to calculate the constants of the following equilibria at 500°C and 1 kbar pressure: TiO2(rutile) + H2O + HCl0 = Ti(OH)3Cl0 (pK = 4.89); TiO2(rutile) + 2HCl0 = Ti(OH)2Cl 2 0 (pK = 4.69), TiO2(rutile) + HS O 4 − + H+ = Ti(OH)2SO 4 0 (pK = 1.98), TiO2(rutile) + 2HSO 4 − + 2H+ = Ti(SO4) 2 0 + 2H2O (pK = −1.50), TiO2(rutile) + 2H2O + OH− = Ti(OH) 5 − (pK = 3.17), TiO2(rutile) + 2H2O + 2OH− = Ti(OH) 6 2− (pK = 1.46), TiO2(rutile) + 2H2O + F− = Ti(OH)3F0 + OH− (pK = 5.86), TiO2(rutile) + 2HF0 = Ti(OH)2F 2 0 (pK = 2.99), and TiO2(rutile) + 2H2O + F− = Ti(OH)4F− (pK = 3.69). Based on the results obtained on the composition of volcanic emanations whose Ti concentrations were determined, we evaluated the constants of the equilibria TiO2(rutile) + H2O + HCl0 = Ti(OH)3Cl0 (pK = 2.74) and TiO2(rutile) + HSO 4 − + H+ = Ti(OH)2SO 4 0 (pK = 3.40) at 25°C. The electrostatic model of electrolyte ionization was used to calculate the ionization constants and the Gibbs free energy values for the following Ti species in aqueous fluids at the parameters of postmagmatic processes: Ti(OH) 3 + , Ti(OH) 4 0 , Ti(OH) 5 − , Ti(OH) 6 2− , Ti(OH)3F0, Ti(OH)2F 2 0 , Ti(OH)4F−, Ti(OH)3Cl0, Ti(OH)2Cl 2 0 , Ti(OH)2SO 4 0 , and Ti(SO4) 2 0 . As follows from our data on Ti complexation with Cl, F, and SO4, fluids the most favorable for Ti migration are aqueous acid F-rich solutions with Ti concentrations of no higher than a few fractions of a milligram per kilogram of water. Original Russian Text ? B.N. Ryzhenko, N.I. Kovalenko, N.I. Prisyagina, 2006, published in Geokhimiya, 2006, No. 9, pp. 950–966.  相似文献   

5.
The infrared (IR) spectra of gem-quality baryte crystals from different occurrences are characterized by relatively weak but strongly pleochroic absorption bands at 3,280, 3,220, 3,155, and 3,115 cm−1. These bands are assigned to anti-symmetric and symmetric OH stretching vibrations of two types of H2O molecules localized on vacant Ba sites. The H–H axis of the H2O I molecule is slightly tilted from the a-axis direction, its twofold axis being nearly parallel to the b-axis, thus defining the plane of the H2O molecule practically parallel to (001). The H2O II molecule has its H–H axis parallel to the b-axis direction, with its plane lying approximately parallel to (101). The values of the total water contents of the baryte crystals, calculated on the basis of IR spectroscopic data, are ranging from about 1.7–3.8 wt.ppm. The possible presence of H3O+ ions is also discussed.  相似文献   

6.
Relative humidity ( P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H2O vibrational modes. The loss of H2O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na+/Ca2+ cations and H2O molecules. The observation of different interactions of H2O molecules and Na+/Ca2+ cations with host aluminosilicate frameworks under high- and low- P\textH 2 \textO P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H2O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm−1 in natrolite, 2,276 cm−1 in scolecite, and 2,176 and 2,259 cm−1 in mesolite) result from strong cation–H2O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na+/Ca2+ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm−1 absorption bands in mesolite also appear to be related to Na+/Ca2+ order–disorder that occur when mesolite loses its Ow4 H2O molecules.  相似文献   

7.
The effect of variations in the rate of ionization of neutral chemical species by cosmic rays, ζ, on the abundances of some observed molecules in the dense cores of dark molecular clouds is studied. Changes in molecular abundances accompanying an increased (decreased) ionization rate have a single origin: the acceleration (deceleration) of processes that are affected directly or indirectlybychemical reactions with charged species. In addition to affecting the gas-phase chemistry, an increased cosmic-ray flux leads to the more efficient destruction of dust-grain mantles and also accelerates the freezing of some components onto dust. In particular, in a model with an increased ζ, the destruction of the volatile N2 molecule by ionized helium leads to the rapid accumulation of nitrogen atoms in dust-phase ammonia, which has a higher desorption energythan N2. As a result, the gas-phase abundance of NH3 and N2H+ decreases significantly. This mechanism can explain the unusual chemical structures of some dense globules, such as B68, where surprisingly low abundances of nitrogen-bearing molecules are observed together with a central drop in the NH3 and N2H+ column densities. Observations of clouds in HCN and HNC lines can discriminate between the two possible origins of the reduced NH3 and N2H+ abundances: an increased cosmic-ray flux or N2 freezing due to the higher desorption energy of this molecule.  相似文献   

8.
Fluid inclusions in garnet, kyanite and quartz from microdiamond-bearing granulites in the Western Gneiss Region, Norway, document a conspicuous fluid evolution as the rocks were exhumed following Caledonian high- and ultrahigh-pressure (HP–UHP) metamorphism. The most important of the various fluid mixtures and daughter minerals in these rocks are: (N2 + CO2 + magnesian calcite), (N2 + CO2 + CH4 + graphite + magnesian calcite), (N2 + CH4), (N2 + CH4 + H2O), (CO2) and (H2O + NaCl + CaCl2 + nahcolite). Rutile also occurs in the N2 + CO2 inclusions as a product of titanium diffusion from the garnet host into the fluid inclusions. Volatiles composed of N2 + CO2 + magnesian calcite characterise the ambient metamorphic environment between HP–UHP (peak) and early retrograde metamorphism. During progressive decompression, the mole fraction of N2 increased in the fluid mixtures; as amphibolite-facies conditions were reached, CH4 and later, H2O, appeared in the fluids, concomitant with the disappearance of CO2 and magnesian calcite. Graphite is ubiquitous in the host lithologies and fluid inclusions. Thermodynamic modelling of the metamorphic volatiles in a graphite-buffered C-O-H system demonstrates that the observed metamorphic volatile evolution was attainable only if the f O2 increased from c. −3.5 (±0.3) to −0.8 (±0.3) log units relative to the FMQ oxygen buffer. External introduction of oxidising aqueous solutions along a system of interconnected ductile shear zones adequately explains the dramatic increase in the f O2. The oxidising fluids introduced during exhumation were likely derived from dehydration of oceanic crust and continental sediments previously subducted during an extended period of continental collision in conjunction with the Caledonian orogeny. Received: 15 December 1997 / Accepted: 25 May 1998  相似文献   

9.
The H2O and H2 solubilities in an albite melt at 1200° C and 2 kbar over the entire range of gas phase composition, from pure hydrogen to pure water were studied in gas-media pressure vessels. The water solubility initially increases with increasing hydrogen content until a maximum of 9.19 wt% H2O atXH 2 v =0.1 is reached, withXH 2 v >0.1 the water solubility decreases. The hydrogen solubility curve has a maximum atXH 2 v =0.42 where the concentration reaches 0.206 wt% H2O. Over the entire compositional range1H NMR (nuclear magnetic resonance) spectra show distinct absorption lines due to protons bound to OH groups and to isolated firmly bound water molecules. In NMR and Raman spectra there were no bands attributable to the H–H vibrations of molecular hydrogen. The X-ray photo-electronic spectra of hydrogen-bearing glasses show the Si2p (99 eV) band which corresponds to the zero-valency silicon. The formation of OH groups and molecular water during interaction between hydrogen-bearing fluids and melts under reducing conditions has a qualitative effect, the same as for water dissolution. Another point of interest is that hydrogen-bearing melts undergo more depolymerization than do hydrous melts.  相似文献   

10.
The speciation of carbon in subseafloor hydrothermal systems has direct implications for the maintenance of life in present-day vent ecosystems and possibly the origin of life on early Earth. Carbon monoxide is of particular interest because it represents a key reactant during the abiotic synthesis of reduced carbon compounds via Fischer-Tropsch-type processes. Laboratory experiments were conducted to constrain reactions that regulate the speciation of aqueous single carbon species under hydrothermal conditions and determine kinetic parameters for the oxidation of CO according to the water water-gas shift reaction (CO2 + H2 = CO + H2O). Aqueous fluids containing added CO2, CO, HCOOH, NaHCO3, NaHCOO, and H2 were heated at 150, 200, and 300 °C and 350 bar in flexible-cell hydrothermal apparatus, and the abundances of carbon compounds was monitored as a function of time. Variations in fluid chemistry suggest that the reduction of CO2 to CH3OH under aqueous conditions occurs via a stepwise process that involves the formation of HCOOH, CO, and possibly CH2O, as reaction intermediaries. Kinetic barriers that inhibit the reduction of CH3OH to CH4 allow the accumulation of reaction intermediaries in solution at high concentrations regulated by metastable thermodynamic equilibrium. Reaction of CO2 to CO involves a two-step process in which CO2 initially undergoes a reduction step to HCOOH which subsequently dehydrates to form CO. Both reactions proceed readily in either direction. A preexponential factor of 1.35 × 106 s−1 and an activation energy of 102 kJ/mol were retrieved from the experimental results for the oxidation of CO to CO2. Reaction rates amongst single carbon compounds during the experiments suggest that ΣCO2 (CO2 + HCO3− + CO32−), CO, ΣHCOOH (HCOOH + HCOO−), and CH3OH may reach states of redox-dependent metastable thermodynamic equilibrium in subseafloor and other hydrothermal systems. The abundance of CO under equilibrium conditions is strongly dependent on temperature, the total carbon content of the fluid, and host-rock lithology. If crustal residence times following the mixing of high-temperature hydrothermal fluids with cool seawater are sufficiently long, reequilibration of aqueous carbon can result in the generation of additional reduced carbon species such as HCOOH and CH3OH, and the consumption of H2. The present study suggests that abiotic reactions involving aqueous carbon compounds in hydrothermal systems are sufficiently rapid to influence metabolic pathways utilized by organisms that inhabit vent environments.  相似文献   

11.
 Incorporation of hydrocarbons (CH4, C2H6, C3H8, C4H10) in cordierite channels was experimentally studied at 700 °C and at pressures from 200 to 1000 MPa, (avoiding recrystallization). The maximum concentrations of hydrocarbons determined by gas chromatographic analysis are CH4=78.3, C2H6=134, C2H4 + C2H6=26, C3H8=28, C4H10=32, C5H12=23, and C6H14=7 × 10−3 wt%). According to IR spectroscopy data, the channel forms of hydrocarbons differ from the forms on the surface. As a result of interactions with the framework oxygen, normal hydrocarbons are converted to saturated oligomers and their fragments. Small amounts of water molecules of the first and second types (up to 0.3 wt%) are formed in the same way. As pressure grows from 200 to 1000 MPa, the total content of structural hydrocarbons is nearly doubled. Special runs on cordierite saturation in mixtures of hydrocarbons with water showed that low contents of hydrocarbons in natural cordierites correspond to their large concentrations in fluid. Received: 7 May 2001 / Accepted: 17 July 2001  相似文献   

12.
The hydrolysis of the Pd2+ ion in HClO4 solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K (1)0 and K (2)0were determined for the reactions Pd2+ + H2O = PdOH+ + H+ and Pd2+ + 2H2O = Pd(OH)20 + 2H+, respectively. The values of log K (1)0 = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K (2)0 = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K (1)0 = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.  相似文献   

13.
Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)40, U(OH)2Cl20, and UOH Cl30 Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO2(aq), −1374.57 for U(OH)2 Cl20, and −1265.49 for UOH Cl30, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO2(cr) = UO2(aq), pK 0 = 6.64; UO2(cr) + 2HCl0 = U(OH)2 Cl20, pK 2 = 3.56; and UO2(cr) + 3HCl0 = UOHcl30 + H2O, pK 3 = 3.05. The value pK 1 ≈ 5.0 was obtained as a first approximation for the equilibrium UO2(cr) + H2O + HCl0 = U(OH)3Cl0. The constant of the reaction UO2(cr) + 4HCl0 = UCl40 + 2H2O (pK 4 = 7.02) was calculated taking into account the ionization constants of U Cl40 and U(OH)40, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO2 + x /UO2 redox pair oxidized Au(cr) to Au+(aq), which was then reduced under the influence of stronger reducers.  相似文献   

14.
The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)4− dominates Al speciation and is formed according to the reaction 0.5 NaAl3Si3O12H2(cr)+2 H2O = 0.5 NaAlSi3O8(cr)+Al(OH)4−+H+. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)40(aq) or NaAl(OH)3Cl(aq)0. The calculated constant for the reaction Al(OH)4−+Na+=NaAl(OH)40(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)3F(aq)0 and NaAl(OH)2F20(aq), according to 0.5 NaAl3Si3O12H2(cr)+Na++HF(aq)0+H2O = 0.5 NaAlSi3O8(cr)+ NaAl(OH)3F(aq)0+H+, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl3Si3O12H2(cr)+Na++2 HF(aq)0 = 0.5 NaAlSi3O8(cr)+NaAl(OH)2F20(aq)+H+, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)2F20(aq) in low-density fluids also increases relative to NaAl(OH)3F(aq)0. These complexes, together with Al(OH)2F(aq)0 and AlOHF20(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.  相似文献   

15.
The polymorphic relations for Mg3(PO4)2 and Mg2PO4OH have been determined by reversed experiments in the temperature-pressure (T-P) range 500–1100 °C, 2–30 kbar. The phase transition between the low-pressure phase farringtonite and Mg3(PO4)2-II, the Mg analogue of sarcopside, is very pressure dependent and was tightly bracketed between 625 °C, 7 kbar and 850 °C, 9 kbar. The high-temperature, high-pressure polymorph, Mg3(PO4)2-III, is stable above 1050 °C at 10 kbar and above 900 °C at 30 kbar. The low-pressure stability of farringtonite is in keeping with its occurrence in meteorites. The presence of iron stabilizes the sarcopside-type phase towards lower P. From the five Mg2PO4OH polymorphs only althausite, holtedahlite, β-Mg2PO4OH (the hydroxyl analogue of wagnerite) and ɛ-Mg2PO4OH were encountered. Relatively speaking, holtedahlite is the low-temperature phase (<600 °C), ɛ-Mg2PO4OH the high-temperature, low-pressure phase and β-Mg2PO4OH the high-temperature, high-pressure phase, with an intervening stability field for althausite which extends from about 3 kbar at 500 °C to about 12 kbar at 800 °C. Althausite and holtedahlite are to be expected in F-free natural systems under most geological conditions; however, wagnerite is the most common Mg-phosphate mineral, implying that fluorine has a major effect in stabilizing the wagnerite structure. Coexisting althausite and holtedahlite from Modum, S. Norway, show that minor fluorine is strongly partitioned into althausite (KD F/OH≈ 4) and that holtedahlite may incorporate up to 4 wt% SiO2. Synthetic phosphoellenbergerite has a composition close to (Mg0.9□0.1)2Mg12P8O38H8.4. It is a high-pressure phase, which breaks down to Mg2PO4OH + Mg3(PO4)2 + H2O below 8.5 kbar at 650 °C, 22.5 kbar at 900 °C and 30 kbar at 975 °C. The stability field of the phosphate end-member of the ellenbergerite series extends therefore to much lower P and higher T than that of the silicate end-members (stable above 27 kbar and below ca. 725 °C). Thus the Si/P ratio of intermediate members of the series has a great barometric potential, especially in the Si-buffering assemblage with clinochlore + talc + kyanite + rutile + H2O. Application to zoned ellenbergerite crystals included in the Dora-Maira pyrope megablasts, western Alps, reveals that growth zoning is preserved at T as high as 700–725 °C. However, the record of attainment of the highest T and/or of decreasing P through P-rich rims (1 to 2 Si pfu) is only possible in the presence of an additional phosphate phase (OH-bearing or even OH-dominant wagnerite in these rocks), otherwise the trace amounts of P in the system remain sequestered in the core of Si-rich crystals (5 to 8 Si pfu) and can no longer react. Received: 7 April 1995 / Accepted: 12 November 1997  相似文献   

16.
A geochemical study of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh, India was carried out using light hydrocarbon compounds to assess the hydrocarbon potential of the basin. Suite of 80 soil samples were collected from the depth of 2.5 m and analyzed for adsorbed light gaseous hydrocarbons namely methane (CH4), ethane (C2H6) and propane (C3H8) in Gas chromatograph. Compound specific Carbon isotope ratios for CH4 and C2H6 were also determined using GC-C IRMS (Gas Chromatograph Combustion Isotope Mass Spectrometer). The presence of moderate to low concentrations of methane (CCH4 C_{CH_4 } : 1 to 138 ppb), ethane (H4{H_4 }: 1 to 35 ppb) and propane (CC3 H8 C_{C_3 H_8 } : 1 to 20 ppb) was measured in the soil samples. Carbon isotopic composition of d13 CCH4 \delta ^{13} C_{CH_4 } ranges between −27.9 to −47.1 ‰ and d13 CC2 H6 \delta ^{13} C_{C_2 H_6 } ranged between −36.9 to −37.2 ‰ (V-PDB) indicating that these gases are of thermogenic origin. Study of soil samples suggests the area has good potential for hydrocarbon.  相似文献   

17.
Summary The crystal structure of arsentsumebite, ideally, Pb2Cu[(As, S)O4]2(OH), monoclinic, space group P21/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?3, Z = 2, dcalc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb2 Me(XO4)2(Z) where Me = Cu2+, Mn2+, Zn2+, Fe2+, Fe3+; X = S, Cr, V, As, P; Z = OH, H2O. Members of this group include tsumebite, Pb2Cu(SO4)(PO4)(OH), vauquelinite, Pb2Cu(CrO4)(PO4)(OH), brackebuschite, Pb2 (Mn, Fe)(VO4)2(OH), arsenbracke buschite, Pb2(Fe, Zn)(AsO4)2(OH, H2O), fornacite, Pb2Cu(AsO4)(CrO4)(OH), and feinglosite, Pb2(Zn, Fe)[(As, S)O4]2(H2O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO6 octahedra and M–T represents corner sharing between octahedra and XO4 tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)2(AsO4)2 (OH, H2O)2 and tsumcorite-group minerals Me(1)Me(2)2(XO4)2(OH, H2O)2. Received June 24, 2000; revised version accepted February 8, 2001  相似文献   

18.
High temperature stability limit of phase egg, AlSiO3(OH)   总被引：1，自引：1，他引：0  
The stability relations of phase egg, AlSiO3(OH), have been investigated at pressures from 7 to 20 GPa, and temperatures from 900 to 1700 °C in a multi-anvil apparatus. At the lower pressures phase egg breaks down according to the univariant reaction, phase egg = stishovite + topaz-OH, which extends from 1100 °C at 11 GPa to 1400 °C at 13 GPa where it terminates at an invariant point involving corundum. At pressures above the invariant point, the stability of phase egg is limited by the breakdown reaction, phase egg = stishovite + corundum + fluid, which extends from the invariant point to 1700 °C at 20 GPa. Stishovite crystallized in the Al2O3-SiO2-H2O system contains Al2O3, and the amount of Al2O3 increases with increasing temperature. It is inferred that the Al2O3 content is controlled by the charge-balanced substitution of Si4+ by Al3+ and H+. Aluminum-bearing stishovite coexisting with an H2O-rich fluid may contain a certain amount of water. Therefore, phase egg and stishovite in a subducting slab could transport some H2O into the deep Earth. Received: 14 October 1998 / Accepted: 19 May 1999  相似文献   

19.
Uraninite solubility in HF solutions (0.0001–0.5 m) was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the predominant U(IV) species in aqueous solution are U(OH)40, U(OH)3F0, and U(OH)2 F20. Using the results of uraninite solubility measurement, the Gibbs free energies of the uranium (IV) species were calculated at 500°C and 1000 bar (kJ/mol): −986.55 for UO2(aq), −1712.42 for U(OH)3F0, −1755.53 for U(OH)2F20, and the equilibrium constants of the uraninite solubility in water and HF solutions were estimated: UO2(κ) = UO2(aq), which is similar to UO2(cr) + 2H2O = U(OH)40, pK0 = 6.64; UO2(cr) + HF0 + H2O = U(OH)3F0, K1 = 0.0513; UO2(cr) + 2HF0 = U(OH)2F20K2 = 7.00 × 10−4. Approximate values K3 = 5.75 × 10−3 and K4 = 6.7 × 10−2 were obtained for equilibria UO2(cr) + 4HF0 =UF40 + 2H2O and UO2(cr) + 4HF = UF40 + 2H2O. Maximum observed in the uranium concentration curve as a function of HF concentration can be explained by the decrease (to < 1) of activity coefficient ratio of HF0 to U(OH)3F0 with increasing HF concentrations.  相似文献   

20.
Summary. ?Ca-tourmaline has been synthesized hydrothermally in the presence of Ca(OH)2 and CaCl2-bearing solutions of different concentration at T = 300–700 °C at a constant fluid pressure of 200 MPa in the system CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthesis of tourmaline was possible at 400 °C, but only above 500 °C considerable amounts of tourmaline formed. Electron microprobe analysis and X-ray powder data indicate that the synthetic tourmalines are essentially solid solutions between oxy-uvite, CaMg3- Al6(Si6O18)(BO3)3(OH)3O, and oxy-Mg-foitite, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O. The amount of Ca ranges from 0.36 to 0.88 Ca pfu and increases with synthesis temperature as well as with bulk Ca-concentration in the starting mixture. No hydroxy-uvite, CaMg3(MgAl5)(Si6O18)(BO3)3(OH)3(OH), could be synthesized. All tourmalines have < 3 Mg and > 6 Al pfu. The Al/(Al + Mg)-ratio decreases from 0.80 to 0.70 with increasing Ca content. Al is coupled with Mg and Ca via the substitutions Al2□Mg−2Ca−1 and AlMg−1H−1. No single phase tourmaline could be synthesized. Anorthite ( + quartz in most runs) has been found coexisting with tourmaline. Other phases are chlorite, tremolite, enstatite or cordierite. Between solid and fluid, Ca is strongly fractionated into tourmaline ( + anorthite). The concentration ratio D = Ca(fluid)/Ca(tur) increases from 0.20 at 500 °C up to 0.31 at 700 °C. For the assemblage turmaline + anorthite + quartz + chlorite or tremolite or cordierite, the relationship between Ca content in tourmaline and in fluid with temperature can be described by the equation (whereby T = temperature in °C, Ca(tur) = amount of Ca on the X-site in tourmaline, Ca( fluid) = concentration of Ca2+ in the fluid in mol/l). The investigations may serve as a first guideline to evaluate the possibility to use tourmaline as an indicator for the fluid composition.
Zusammenfassung. ?Synthese von Ca-Turmelin im System CaO-MgO-Al 2 O 3 -SiO 2 -B 2 O 3 -H 2 O-HCl Im System CaO-MgO-Al2O3-SiO2-B2O3-H2O-HCl wurde Ca-Turmalin hydrothermal aus Ca(OH)2 and CaCl2-haltigen L?sungen bei T = 300–700 °C und einem konstanten Fluiddruck von 200 MPa synthetisiert. Die Synthese von Turmalin war m?glich ab 400 °C, aber nur oberhalb von 500 °C bildeten sich deutliche Mengen an Turmalin. Elektronenstrahl-Mikrosondenanalysen und R?ntgenpulveraufnahmen zeigen, da? Mischkristalle der Reihe Oxy-Uvit, CaMg3Al6(Si6O18)(BO3)3(OH)3O, und Oxy-Mg-Foitit, □(MgAl2)Al6(Si6O18)(BO3)3(OH)3O gebildet wurden. Der Anteil an Ca variiert zwischen 0.36 und 0.88 Ca pfu und nimmt mit zunehmender Synthesetemperatur und zunehmender Ca-Konzentration im System zu. Hydroxy-Uvit, CaMg3(MgAl5) (Si6O18)(BO3)3(OH)3(OH), konnte nicht synthetisiert werden. Alle Turmaline haben < 3 Mg und > 6 Al pfu. Dabei nimmt das Al/(Al + Mg)- Verh?ltnis mit zunehmendem Ca-Gehalt von 0.80 auf 0.70 ab. Al ist gekoppelt mit Mg und Ca über die Substitutionen Al2□Mg−2Ca−1 und AlMg−1H−1. Einphasiger Turmalin konnte nicht synthetisiert werden. Anorthit (+ Quarz in den meisten F?llen) koexistiert mit Turmalin. Andere Phasen sind Chlorit, Tremolit, Enstatit oder Cordierit. Ca zeigt eine deutliche Fraktionierung in den Festk?rpern Turmalin (+ Anorthit). Das Konzentrationsverh?ltnis D = Ca(fluid)/Ca(tur) nimmt von 0.20 bei 500 °C auf 0.31 bei 700 °C zu. Für die Paragenese Turmalin + Anorthit + Quarz mit Chlorit oder Tremolit oder Cordierit gilt folgende Beziehung zwischen Ca-Gehalt in Turmalin und Fluid und der Temperatur: (wobei T = Temperatur in °C, Ca(tur) = Anteil an Ca auf der X-Position in Turmalin, Ca(fluid) = Konzentration von Ca2+ im Fluid in mol/l). Die Untersuchungen dienen zur ersten Absch?tzung, ob Turmalin als Fluidindikator petrologisch nutzbar ist.

Received July 24, 1998;/revised version accepted October 21, 1999  相似文献   

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