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.     

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.     

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.     

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).     

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.     

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.     

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.     

Polycyclic aromatic hydrocarbons in surface sediments of Binacional Itaipu Lake,Brazil: characteristics,sources and toxicity evaluation

Itaipu Lake, which includes the Itaipu hydroelectric power plant, is one of the largest dams in the world and has a strong relationship with its surroundings. The flooded area has multiple uses such as navigation, recreation, water abstraction for industrial, urban and agricultural irrigation. The lake is located at the frontier between Brazil, Argentina and Paraguay. In this study, superficial sediments collected from nine sampling sites were analysed for grain size, organic matter and 16 priority polycyclic aromatic hydrocarbons (PAHs) using high-performance liquid chromatography (HPLC) with fluorescence detector. The total concentration of PAHs in the dry sediment ranged from 35.21 to 685.37 µg kg^?1. Diagnostic ratios showed that the possible source of PAHs in the Itaipu Lake could be pyrolitic and petrogenic. The potential toxicity of sediment of PAHs varied from not detected to 127.70 µg g^?1, suggesting that some adverse ecological effects would arise due to PAHs in these sediments.     

A Sm-Nd isotopic study of the South Harris Igneous Complex,the Outer Hebrides

Sm-Nd geochronology may be used to bracket the age of metamorphism in rocks which are difficult to date by other methods. By coupling whole rock Sm-Nd analyses of the principal members of the South Harris Igneous Complex, with Sm-Nd mineral isochrons on two anothositic gabbros, the age of granulite facios metamorphism has been defined. Whole rock analyses of three pairs of closely spaced samples of the anorthosite give consistent ages averaging 2.18±0.06 Gyr, but in general the data from the anorthosite do not define an isochron as a result of variable contamination of the evolving magma chamber. Whole rock data on the tonalite indicate that it is younger than 2.06 Gyr; its mean T_CHUR age is 1.86±0.05 Gyr. Garnet-pyroxene-amphibole-plagioclase mineral isochrons on two anorthosite samples give identical 1.87±0.04 Gyr ages which date cooling after the high pressure granulite facies metamorphism. Together with the tonalite whole rock data this defines the age of that metamorphism and confirms Dearnley's original assignment of an early Laxfordian age.     

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.     

Competition for the general cargo transports of Sweden's foreign trade

The object of the paper is to analyze changes in modal and port allocation of general cargo flows in Sweden's foreign trade between 1960 and 1976. It summarizes some results of a forthcoming report on the project ‘Tendencies in Liner Shipping’ financed by the ‘Transport Research Delegation’, Stockholm.     

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.     

Levels and distributions of polycyclic aromatic hydrocarbons (PAHs) in middle reach of Huaihe River,China: anthropogenic influences and ecological risks

Polycyclic aromatic hydrocarbons (PAHs) are a group of aromatic hydrocarbons with high toxicity to human health. PAH emissions from industrial activities have become the primary sources of PAH contamination in Chinese watersheds. Here, we analyzed 10 individual priority PAHs in 120 water samples taken from middle reach of Huaihe River, China. The results show that the PAH levels in studied watershed are significantly lower as compared to other Chinese watersheds, approaching or slightly exceeding the PAH levels in watersheds from selected European and North American countries. We observe rather large variation in spatial and vertical PAH distributions, pointing to PAH inputs from local industrial emissions, and PAH cycle among atmosphere, water and sediment. Individual PAH ratios (i.e., phenanthrene/anthracene and fluorene/pyrene) and principal components analysis suggest a primarily pyrolytic PAH sources (combustion of coal and coke) in water column. Other accompanying PAH sources include emissions from steel industry and gasoline. Total toxic benzo[a]pyrene equivalent of PAHs in studied water column indicates that PAHs in watershed of middle reach of Huaihe River pose limited toxicity to the environment.     

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.     

Shoreline erosion rates along barrier islands of the north central gulf of Mexico

Rates of shoreline change and overwash penetration distances were calculated for barrier islands along the Louisiana, Mississippi, and Alabama coasts with the orthogonal grid mapping system (OGMS). Average rates of shoreline change are exceptionally high in Louisiana, being of the order ?4.7 to ?7.4 m yr^?1. Mississippi and Alabama recession rates are lower and range from ?2.0 to ?3.1 m yr^?1 over the period of record. Erosion rates along the shorelines of these islands have remained relatively constant over the period of study with five exceptions in coastal Louisiana and the Chandeleur-Breton Islands Arc, and two exceptions along the Mississippi-Alabama barrier islands where they have accelerated. Mean overwash penetration is greatest along Dauphin Island, Alabama, and Cat Island, Mississippi: 207.6 and 197.9 m, respectively. The Chandeleur-Brenton Islands Arc range from 88.1 m at the central barrier to 180.4 along the flanks. The Mississippi islands range from 105.2 m on Ship Island to 200.5 m along central Horn Island. Mean overwash penetration along the Louisiana barriers is highly variable: 46.3 to 211.4 m.     

A MEG study of the olivine and spinel forms of Mg2SiO4

In this paper we present a theoretical investigation of the structures and relative stability of the olivine and spinel phases of Mg₂SiO₄. We use both a purely ionic model, based on the Modified Electron Gas (MEG) model of intermolecular forces, and a bond polarization model, developed for low pressure silica phases, to investigate the role of covalency in these compounds. The standard MEG ionic model gives adequate structural results for the two phases but incorrectly predicts the spinel phase to be more stable at zero pressure. This is mainly because the ionic modeling of Mg₂SiO₄ only accounts for 95 percent of the lattice energy. The remainder can be attributed to covalency and many-body effects. An extension of the MEG ionic model using “many-body” pair potentials corrects the phase stability error, but predicts structures which are in poorer agreement with experiment than the standard ionic approach. In addition, calculations using these many-body pair potentials can only account for 10 percent of the missing lattice energy. This model predicts an olivine-spinel phase transition of 8 GPa, below the experimental value of 20 GPa. Therefore, in order to understand more fully the stability of these structures we must consider polarization. A two-shell bond polarization model enhances the stability of both structures, with the olivine structure being stabilized more. This model predicts a phase transition at about 80 GPa, well above the observed value. Also, the olivine and spinel structures calculated with this approach are in poorer agreement with experiment than the ionic model. Therefore, based on our investigations, to properly model covalency in Mg₂SiO₄, a treatment more sophisticated than the two-shell model is needed.     

Density constraints on the formation of the continental Moho and crust

The densities of mantle magmas such as MORB-like tholeiites, picrites, and komatiites at 10 kilobars are greater than densities for diorites, quartz diorites, granodiorites, and granites which dominate the continental crust. Because of these density relations primary magmas from the mantle will tend to underplate the base of the continental crust. Magmas ranging in composition from tholeiites which are more evolved than MORB to andesite can have densities which are less than rocks of the continental crust at 10 kilobars, particularly if they have high water contents. The continental crust can thus be a density filter through which only evolved magmas containing H₂O may pass. This explains why primary magmas from the mantle such as the picrites are so rare. Both the over-accretion (i.e., Moho penetration) and the under-accretion (i.e., Moho underplating) of magmas can readily explain complexities in the lithological characteristics of the continental Moho and lower crust. Underplating of the continental crust by dense magmas may perturb the geotherm to values which are characteristic of those in granulite to greenschist facies metamorphic sequences in orogenic belts. An Archean continental crust floating on top of a magma flood or ocean of tholeiite to komatiite could have undergone a major cleansing process; dense blocks of peridotite, greenstone, and high density sediments such as iron formation could have been returned to the mantle, granites sweated to high crustal levels, and a high grade felsic basement residue established.     

Calorimetric study of the stability of spinelloids in the system NiAl2O4-Ni2SiO4

Enthalpies of solution in molten 2 PbO · B₂O₃ at 974 K were measured for four spinelloids, phases I (0.75 NiAl₂O₄ · 0.25 Ni₂SiO₄), II (0.60 NiAl₂O₄ · 0.40 Ni₂SiO₄), III and IV (0.50 NiAl₂O₄ · 0.50 Ni₂SiO₄) in the system NiAl₂O₄ · Ni₂SiO₄. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl₂O₄ and Ni₂SiO₄ spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl₂O₄ and Ni₂SiO₄ spinels were estimated (in cal mol^?1 K^?1): phase I, 1.2; phase II, 1.5; phase III, 2.0–2.3; phase IV, 3.0–3.1. The thermochemical data obtained above suggest that the spinelloids are “entropy-stabilized” phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist.     

The effect of crystal field stabilization on the olivine→spinel transition in the system Mg2SiO4 - Fe2SiO4

Crystal field stabilization (CFS) plays a significant role in determining equilibrium phase boundaries in olivine→spinel transformations involving transition-metal cations, including Fe²⁺ which is a major constituent of the upper mantle. Previous calculations for Fe₂SiO₄ ignored pressure and temperature dependencies of crystal field stabilization enthalpies (CFSE) and the electronic configurational entropy (S _CFS). We have calculated free energy changes (ΔG _CFS) due to differences of crystal field splittings between Fe₂SiO₄ spinel and fayalite from: ΔG _CFS=?ΔCFSE?TΔS _CFS, as functions of P and T, for different energy splittings of t _2g orbital levels of Fe²⁺ in spinel. The results indicate that ΔG _CFS is always negative, suggesting that CFS always promotes the olivine→spinel transition in Fe₂SiO₄, and expands the stability field of spinel at the expense of olivine. Because of crystal field effects, transition pressures for olivine→spinel transformations in compositions (Mg_1?x Fe _x )₂SiO₄ are lowered by approximately 50x kbar, which is equivalent to having raised the olivine→spinel boundary in the upper mantle by about 15 km.     

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.