Carbon on surfaces of magnesium oxide and olivine single crystals. Diffusion from the bulk or surface contamination?

We have conducted detailed studies of the behavior of carbon on the surfaces of MgO and olivine single crystals using various surface analytical techniques: viz. secondary ion mass spectrometry (SIMS), Auger electron spectrometry (AES) and X-ray photoelectron spectrometry (XPS). In order to distinguish without ambiguity the effect of diffusion of carbon from the bulk to the surface and the effect of surface contamination by carbon-containing species, the experiments were conducted in ultrahigh vacuum, i.e. 10^?11–10^?9 torr. In addition to MgO and olivine single crystals, we have conducted the same studies on TiO₂, MnO, SiO₂ and Ta₂O₅ which serve as blank samples. The MgO and olivine samples were also intentionally implanted with known doses of carbon and the mobility of this particular carbon was investigated in detail. Our results show that the bulk carbon content in MgO is around 40 wt. ppm, considerably lower than the quantities quoted by Freund and co-workers in the past. We also show that the carbon in both MgO and olivine does not display any rapid diffusion behaviour leading to surface segreation in the temperature range 78–723 K, in contrast to the previous findings of Freund and co-workers.     

Infrared spectra of olivine polymorphs: α, β phase and spinel

Infrared (IR) absorption spectra are presented for olivine (α) and spinel (γ) phases of A₂SiO₄ (A=Fe, Ni, Co) and Mg₂GeO₄. IR spectra of β phase (“modified spinel”) Co₂SiO₄ and of α Mg₂SiO₄ are also included. These results provide reference spectra for the identification of olivine high-pressure polymorphs. Isostructural and isochemical correlations are used to support a general interpretation of the spectra and to predict the spectrum of γ Mg₂SiO₄. A γ Mg₂GeO₄ sample equilibrated at 1,000° C shows evidence of partial inversion, but one equilibrated at 730° C does not. This suggests that partial inversion could occur in silicate spinels at elevated temperatures and pressures, however no evidence of inversion is seen in the ir spectra of the silicates in this study.     

Infrared vibrational spectra of Beta-Phase Mg2SiO4 and Co2SiO4 to Pressures of 27 GPa

Infrared absorption spectra of the high-pressure polymorphs β-Mg₂SiO₄ and β-Co₂SiO₄ have been measured between 0 and 27 GPa at room temperature. Grüneisen parameters determined for 11 modes of β-Mg₂SiO₄ (frequencies of 300 to 1,050 cm^?1) and 5 modes of β-Co₂SiO₄ (490 to 1,050 cm^?1) range between 0.8 and 1.9. Averaging the mid-infrared spectroscopic data for β-Mg₂SiO₄ yields an average Grüneisen parameter of 1.3 (±0.1), in good agreement with the high-temperature thermodynamic value of 1.35. Similarly, we find a value of 1.05 (±0.2) for the average spectroscopic Grüneisen parameter of β-Co₂SiO₄.     

Crystal structures of Ni2SiO4 and Fe2SiO4 as a function of temperature and heating duration

X-ray structure refinements of Ni₂SiO₄ and Fe₂SiO₄ spinels have been made as a function of temperature and heating duration by intensity measurements at high temperatures and room pressure. The lattice parameters of Ni₂SiO₄ spinel linearly increased with temperature up to 1,000° C. However, Fe₂SiO₄ spinel exhibited a nonlinear thermal expansion and was converted to a polycrystalline mixture of spinel and olivine by heating of less than one-hour at 800° C. The ratios between the octahedral and tetrahedral bond lengths D _oct/D _tetr and between the shared and unshared edge distances (O-O)_sh/(O-O)_unsh in Fe₂SiO₄ spinel were both much larger than those in Ni₂SiO₄. These ratios increase with temperature. The Fe₂SiO₄ spinel more readily approached a activation state which facilitated the transition to the olivine structure than the Ni₂SiO₄ spinel. The lattice parameter of Ni₂SiO₄ spinel decreased with heating period at constant temperatures of 700° C and 800° C. The parameter of the quenched sample after heating for 52 h at 700° C was smaller than that of the nonheated sample. The refinements of the site occupancies at each heating duration indicated an increase in the cation deficiency in both tetrahedral and octahedral sites. Electron microprobe analysis, however, proved no significant difference in the chemical compositions between the quenched and nonheated samples. Si and Ni atoms displaced from normally occupied spinel lattice sites are assumed to settle in vacant sites defined by the cubic close packed oxygen sublattice in a manner which preserves the electric neutrality of the bulk crystal.     

On the Relationship between Refractive Index and Density for SiO2-polymorphs

Five different refraction formulas were applied to SiO₂ polymorphs in order to determine the most suitable refractive index-density relation. 13 SiO₂ polymorphs with topological different tetrahedral frameworks are used in this study including eight new low density SiO₂ polymorphs — so called “guest free porosils”. These SiO₂ polymorphs cover a density range from 1.76 to 2.92 g/cm³. The mean refractive indices (ovn) of the porosils have been determined by the immersion method, the densities (ρ) were calculated from the unit cell parameters. Assuming the polarizability (α) of all SiO₂ polymorphs to be constant the general refractivity formula $$\{ 2\overline {11} 0\} \langle 0001\rangle $$ turned out to be the most suitable for SiO₂ polymorphs. Regression analysis yields an electronic overlap parameter b=1.2(1).     

Electrical conductivity measurements on olivines and pyroxenes under defined thermodynamic activities as a function of temperature and pressure

Electrical conductivities of Ni₂SiO₄, Fe₂SiO₄, and MgSiO₃ were measured on synthetic powders in the temperature range 340° to 1,100° C and at pressures up to 20 kbars. For ternary compounds such as olivines and pyroxenes the control of two further variables, like the chemical activities of two components are needed, besides temperature and pressure. The activities of the corresponding binary oxides were controlled by equilibrating the samples with their neighbour-phases. Control of the oxygen partial pressure was achieved by buffer techniques. From the slopes of the lg σ vs. 1/T lines the activation energies were calculated for 10 kbar: 0.56 eV and 2.7 eV for Ni₂SiO₄ in equilibrium with SiO₂ and Ni/NiO-buffer for the temperature range 500°–800°C and 800°–1,000°C resp. 0.52 eV for Fe₂SiO₄ in equilibrium with SiO₂ and metallic iron, and 0.38 eV in equilibrium with SiO₂ and magnetite; 1.11 eV for MgSiO₃ in equilibrium with SiO₂, and 1.25 eV in equilibrium with Mg₂SiO₄.     

Some physical properties of amorphous SiO2 synthesized by shock compression of α quartz

The amorphous phase of SiO₂ produced upon recovery of shock-compressed quartz demonstrates a wide range of refractive indices which can be correlated to the shock state. Both infra-red absorption spectra and X-ray diffraction patterns indicate that the shock-produced amorphous SiO₂ has a statistically more-random atomic distribution and longer Si-O and shorter Si-Si separation than does fused silica. By accounting for phase transformation, the calculated values of the shock and residual temperature are much higher than those obtained by Wackerle (1962) to a pressure of 700 kbar. Our results are consistent with experimental ones.     

Decomposition of fayalite (Fe2SiO4) in an oxygen potential gradient at 1,418 K

The decomposition of fayalite (Fe₂SiO₄) in oxygen potential gradients is studied at T=1,418 K. The compound will be decomposed into its component oxides wüstite, Fe_1?δO, and silica, SiO₂, by the simultaneous action of two different oxygen partial pressures, exceeding a critical ratio, despite the fact that fayalite is stable at both the lower and the higher oxygen potential. A quantitative analysis of the decomposition process caused by defect fluxes within the bulk Fe₂SiO₄ is given.     

Phonon spectra and rigid-ion model calculations on andalusite

Polarised Raman and infrared spectra of (ir) andalusite (Al₂SiO₅) single crystals have been measured and interpreted on the basis of a rigid-ion model calculation. The Al-O bond strength is found to be about 70% ionic in character whereas the mainly covalently bound SiO₄ tetrahedra show ca. 40% ionicity. The interatomic short range forces are strongest between silicon and oxygen and rather weak around the fivefold coordinated aluminium. Thermal soft modes appear above 200°C and are correlated with a weakening of the Al-O bonds.     

Raman scattering and lattice vibrations of Ni2SiO4 spinel at elevated temperature

Raman spectra of Ni₂SiO₄ spinel (O _h ⁷ Z=8) have been measured in the temperature range from 20 to 600 °C and the Raman active vibrations (A _1g +E _g +3F _2g ) have been assigned. A calculation of the optically active lattice vibrations of this spinel has been made, assuming a potential function which combines general valence and short range force constants. The values of the force constants at 20 and 500 °C have been calculated from the vibrational frequencies of the observed Raman spectra and infrared (IR) spectral data. The Ni spinel at 20 °C has a prominently small Si-O bond stretching force constant of K(SiO)=2.356 ～ 2.680 md/Å and a large Ni-O bond stretching constant of K(NiO)=0.843 ～ 1.062 md/Å and these force constants at 500 °C decrease to K(SiO)=2.327 ～ 2.494 md/Å and K(NiO)=0.861 ～ 0.990 md/Å. The Si-O bond is noticeably weakened at high temperatures, despite the small thermal expantion from 1.657 Å (20 °C) to 1.660 Å (500 °C). These changes of the interatomic force constants of the spinel at high temperatures are in accord with the thermal structure changes observed by X-ray diffraction study. The weakened Si-O bond is consistent with the fact that Si atoms in the spinel lattice can diffuse at significant rates at elevated temperature.     

Synthetic Mn3+-kyanite and viridine, (Al2-xMn x 3+ ) SiO5, in the system Al2O3-MnO-MnO2-SiO2

Experiments on the join Al₂SiO₅-“Mn₂SiO₅” of the system Al₂O₃-SiO₂-MnO-MnO₂ in the pressure/temperature range 10–20 kb/900–1050° C with gem quality andalusite, Mn₂O₃, and high purity SiO₂ as starting materials and using /_O2-buffer techniques to preserve the Mn³⁺ oxidation state had following results: At 20 kb/1000°C orange-yellow kyanite mixed crystals are formed. The kyanite solid solubility is limited at about (Al_1.88Mn _0.12 ³⁺ )SiO₅ and, thus, equals approximately that on the join Al₂SiO₅-“Fe₂SiO₅” (Langer and Frentrup, 1973) indicating that there is no Jahn-Teller stabilisation of Mn³⁺ in the kyanite matrix. 5 mole % substitution causes the kyanite lattice constants a _o, b _o, c _o, and V _o to increase by 0.015, 0.009, 0.014 Å, and 1.6 ų, resp., while α, β, γ, remain unchanged. Between 10 and 18 kb/900°C, Mn³⁺-substituted, strongly pleochroitic (emeraldgreen-yellow) andalusite_ss (viridine) was obtained. At 15 kb/900°C, the viridine compositional range is about (Al_1.86Mn _0.14 ³⁺ )SiO₅-(Al_1.56Mn _0,44 ³⁺ )SiO₅. Thus, Al→Mn³⁺ substitutional degrees are appreciably higher in andalusite than in kyanite, proving a strong Jahn-Teller effect of Mn³⁺ in the andalusite structure, which stabilises this structure type at the expense of kyanite and sillimanite and, thus, enlarges its PT-stability range extremely. 17 mole % substitution cause the andalusite constants a _o, b _o, c _o, and V _o to increase by 0.118, 0.029, 0.047 Å and 9.4 ų, resp. At “Mn₂SiO₅”-contents smaller than about 7 mole %, viridine coexists with Mn-poor kyanite. At “Mn₂SiO₅”-concentrations higher than the maximum kyanite or viridine miscibility, braunite (tetragonal, ideal formula Mn²⁺Mn³⁺[O₈/Si0₄]), pyrolusite and SiO₂ were found to coexist with the Mn³⁺-saturated ky _ss or and _ss, respectively. In both cases, braunites were Al-substituted (about 1 Al for 1 Mn³⁺). Pure synthetic braunites had the lattice constants a _o 9.425, c _o, 18.700 Å, V _o 1661.1 ų (ideal compn.) and a _o 9.374, c _o 18.593 ų, V _o 1633.6 ų (1 Al for 1 Mn³⁺). Stable coexistence of the Mn²⁺-bearing phase braunite with the Mn⁴⁺-bearing phase pyrolusite was proved by runs in the limiting system MnO-MnO₂-SiO₂.     

Charge distribution from least-energy structure in Ca - Mg orthosilicates

Calcium-olivine, γ-Ca₂SiO₄, larnite, β-Ca₂SiO₄, merwinite, Ca₃Mg(SiO₄)₂, and monticellite, CaMgSiO₄, are considered. According to a rigid oxyanion scheme, eulerian orientation angles of the SiO₄ tetrahedra and translation coordinates of Ca and Si atoms are specified as structural variables τk. All derivatives of the static energy (Born model) contain atomic charges and repulsive parameters as unknowns; the minimum energy conditions ?E _L/?τ_k=0 yield 34 equations which are solved by a least-squares method. The set of energy parameters fitting structural properties of all four phases together is: z _Ca=1.50, z _o=?1.10 e, r _Ca=1.05, ρ=0.25 Å; the Mg charge was fixed at 1.38 e, from a previous study on forsterite. An average shift of 0.04 Å is observed between experimental and least-energy calculated atomic positions. Results are compared with those of Mg₂SiO₄, where the fit was based both on thermoelastic and on structural properties. If no charge values were fixed “a priori”, just ratios between charges could be determined by fitting them to structural data only.     

Study of pocyclic aromatic hydrocarbons at a pressure of 6–9 GPa with X-ray diffraction and synchrotron radiation

This work is one of the stages of study of the deep C-O-H fluid and investigates the behavior of polycyclic aromatic hydrocarbons (PAHs) under conditions of the Earth’s mantle. The composition of the C-O-H fluid in the upper mantle is estimated as a mixture of H₂O and CH₄ with a minor amount of H₂ and heavier hydrocarbons. Some theoretical calculations show that the stability of heavy hydrocarbons (alkanes, alkenes, and PAHs) increases with an increase in temperature. This paper presents the results of an XRD study of PAHs stability in multianvil presses on a Spring-8 accelerator (Japan). The primary compositions were chosen according to the abundance of PAHs in nature. In situ diffraction spectrums were recorded to determine the PAHs stability field. It was established that the PAHs become unstable at a pressure of 6–9 GPa and a temperature of 873–1073 K.     

Phylogenetic Problems in Polynesian Simuliidae (Diptera: Culicomorpha): A progress report

As a basis for eventual control of the vicious anthropophilic and ornithophilic simuliid females of the Marquesas Islands, a taxonomic revision of Polynesian Simuliidae is in progress. Cytotaxonomic studies reveal two simuliid species in Rarotonga, Cook Islands; nine species in Tahiti, Society Islands, and two in the Marquesas Islands. A cytophylogeny is now available. Polynesian Simuliidae are unique in possessing heterogametic females. A reconstructed phylogeny, based mainly on morphological character states of larvae and pupae, agrees well with the cytophylogeny. One of the new species which is closely related to Simulium oviceps Edwards has larvae with highly reduced, non-functional cephalic fans. Ages of the Polynesian islands are discussed in relation to possible dispersal of Simuliidae into Polynesia.     

Vibrational spectra of olivine composition glasses: The Mg-Mn join

The vibrational frequencies of a series of splatquenched, olivine glasses spanning the compositional range from Mg₂SiO₄ to Mn₂SiO₄ have been determined using both infrared and Raman spectroscopies. The spectra of all glasses show evidence of tetrahedral coordination of silicon (possibly with some slight distortions), and largely octahedral coordination of magnesium. Spectra of Mn-rich glasses indicate that there is some manganese in 4 or 5-fold coordination. The frequencies observed for the fundamental vibrations of the silica tetrahedra are similar to those previously observed for SiO₄ groups in both crystalline and glassy orthosilicates. Additionally, there is evidence for a small amount of silicate polymerization in all glasses characterized: vibrations attributable to Si₂O₇ groups are visible in both infrared and Raman spectra.     

Interaction between fluorine and silica in quenched melts on the joins SiO2-AlF3 and SiO2-NaF determined by raman spectroscopy

The solubility mechanism of fluorine in quenched SiO₂-NaF and SiO₂-AlF₃ melts has been determined with Raman spectroscopy. In the fluorine abundance range of F/(F+Si) from 0.15 to 0.5, a portion of the fluorine is exchanged with bridging oxygen in the silicate network to form Si-F bonds. In individual SiO₄-tetrahedra, one oxygen per silicon is replaced in this manner to form fluorine-bearing silicate complexes in the melt. The proportion of these complexes is nearly linearly correlated with bulk melt F/(F+Si) in the system SiO₂-AlF₃, but its abundance increases at a lower rate and nonlinearly with increasing F/(F+Si) in the system SiO₂-NaF. The process results in the formation ofnonbridging oxygen (NBO), resulting in stabilization of Si₂O ₅ ^2? units as well as metal (Na⁺ or Al³⁺) fluoride complexes in the melts. Sodium fluoride complexes are significantly more stable than those of aluminum fluoride.     

Intrinsic oxygen Fugacity measurements on chromites from the Bushveld Complex and their petrogenetic significance

Oxygen Fugacity measurements were carried out on chromites from the Eastern Bushveld Complex (Maandagshoek) and are compared with former measurements on chromites from the western Bushveld Complex (Zwartkop Chrome Mine). These results together with those of Hill and Roeder (1974) yield the following conditions of formation for the massive chromitite layers: Western Bushveld Complex (Zwartkop Chrome Mine) $$\begin{gathered} Layer{\text{ }}T(^\circ C) p_{O_2 } (atm) \hfill \\ LG3{\text{ 1160}} - {\text{1234 10}}^{ - {\text{5}}} - 10^{ - 7.6} \hfill \\ LG4{\text{ 1175}} - {\text{1200 10}}^{ - 6.35} - 10^{ - 7.20} \hfill \\ LG6{\text{ 1162}} - {\text{1207 10}}^{ - 6.20} - 10^{ - 7.50} \hfill \\ \hfill \\ \end{gathered} $$ Eastern Bushveld Complex (Farm Maandagshoek) $$\begin{gathered} {\text{LXI 1115}} - {\text{1150 10}}^{ - 7.80} - 10^{ - 8.80} \hfill \\ ( = {\text{Steelpoort Seam)}} \hfill \\ {\text{LX 1125 10}}^{ - 8.25} \hfill \\ {\text{V 1120 10}}^{ - 8.55} \hfill \\ {\text{LII 1120 10}}^{ - 8.0} - 10^{ - 8.60} \hfill \\ \end{gathered} $$ The comparison of the data shows, that the chronitite layers within each particular sequence were formed under approximately identicalp _{o 2}- andT-conditions. The chromites from the western Bushveld Complex, however, were formed at higher temperatures and higher oxygen fugacities than the chromites from the eastern Bushveld Complex. Fromp _{o 2}-T-curves of disseminated chromites and the temperatures derived above, the following conditions of formation for the host rocks were obtained: Western Bushveld Complex $$T = 1200^\circ {\text{C; }}p_{{\text{o}}_{\text{2}} } = 10^{ - 7.25} - 10^{ - 7.50} $$ Eastern Bushveld Complex $$T = 1125^\circ {\text{C; }}p_{{\text{o}}_{\text{2}} } = 10^{ - 8.50} - 10^{ - 9.25} $$ Consequently, the host rocks in the Zwartkop-Chrome-Mine, were formed under higher temperatures and higher oxygen fugacities than the host rocks at Maandagshoek. The rock sequence in the Zwartkop-Chrome-Mine therefore originated in an earlier stage of the differentiation of the Bushveld magma. Comparison of the chromites from the host rocks with the chromites from massive layers supports Ulmer's (1969) thesis that an increase of the oxygen fugacity is responsible for the formation of massive chromitite layers. The values in this investigation show that increases of only about 0.5–1.0 log units are necessary to enhance chromitite layer formation.     

Effects of pH on isotherm modeling and cation competition for Cd(II) and Cu(II) biosorption on Myriophyllum spicatum from aqueous solutions

The biosorption characteristics of Cd(II) and Cu(II) ions from aqueous solutions obtained using submerged aquatic plant (Myriophyllum spicatum) biomass were investigated in terms of equilibrium, kinetics, thermodynamics, and cation competition. Langmuir and Freundlich models were applied to describe the biosorption isotherm of metal ions by M. spicatum biomass and isotherm constants considering the most important parameter, pH. The variation of sorption isotherm constants showed pH dependence. The Langmuir and Freundlich models fitted the equilibrium data well. The maximum biosorption capacity (q _m) of M. spicatum biomass was determined to be 29.07 mg/g for the Cd(II) ion at pH 5.0 and 12.12 mg/g for the Cu(II) ion at pH 6.0. Chi square analysis showed that the Freundlich model fitted the equilibrium data better than the Langmuir isotherm. Competition of Cd(II) and Cu(II) in a binary solution showed that the Langmuir monolayer capacity of Cd(II) decreased from 29.07 mg/g with only Cd(II) in solution to 12.02 mg/g in the presence of Cu(II). Kinetics results showed that the biosorption processes of both metal ions followed the pseudo-second-order kinetics well. The calculated thermodynamic parameters (?G ⁰, ?H ⁰, and ?S ⁰) showed that biosorption of Cd(II) and Cu(II) ions onto M. spicatum biomass was feasible, spontaneous, and endothermic in nature. Fourier transform infrared spectroscopy spectrum analysis revealed that Cd(II) and Cu(II) sorption was mainly ascribed to carboxyl, hydroxyl, amine, and C–N groups in M. spicatum.     

Exoelectron spectroscopy of traps in surface layers of phenakite and quartz

The possibilities of exoelectron spectroscopy to investigate defects in dielectrics are demonstrated for phenakite Be₂SiO₄, its structural analogs Zn₂ SiO₄, Be₂GeO₄, solid solutions Be₂Si_1?x Ge _x O₄ (x=0÷1) and α-quartz. Emission maxima at 330 and 670 K in phenakite have been found to be due to [GeO₄]^5? andE' centers, respectively. Structural disturbances in the silicon and oxygen positions have been shown to control the exoemission activity of the crystals. Radiation induced decrease of exoemission activity connected with generation ofE' centers by neutron irradiation has been discovered. The energy level scheme of active centers in the subsurface region of Be₂SiO₄ has been established.     

Zircon and sphene as fission track geochronometer and geothermometer: A reappraisal

The data published earlier on zircon and sphene fission track ages and annealing are discussed in the light of different etching conditions used for age determination and annealing experiments in order to explain the age discordances of some zircon and sphene pairs, as well as numerous closing temperatures obtained for individual minerals. Using the new set of simple etching conditions, zircon (KOH melt) and sphene (HF+HCl), the annealing experiments indicate that tracks in sphene are annealed more easily than in zircon. The closing temperature of zircon and sphene have been calculated at 300° and 250° C respectively. The study reveals that both the fission track age and the closing temperature of a mineral can vary considerably if different etchants are used. For different etching conditions the closing temperatures (T) of sphene have the following order: ^T NaOH> ^T HF+HCl+HNO₃+H₂O> ^THF+HCl>^THCl. An alternative method can be used to obtain thermal histories of rocks by selectively applying various etchants on the same mineral.