Structural control of polyhedral compression in synthetic braunite, Mn2+Mn3+ 6O8SiO4

The compression of synthetic braunite, Mn²⁺Mn³⁺ ₆O₈SiO₄, was studied by high-pressure single-crystal X-ray diffraction carried out in a diamond-anvil cell. The equation of state at room temperature (third-order Birch-Murnaghan equation of state: V ₀=1661.15(8) ų, K _0,298=180.7±0.9 GPa, K′=6.5±0.3) was determined from unit-cell volume data to 9.18 GPa. Crystal structures were determined at 6 different pressures to 7.69 GPa. Compression of the structure (space group I4₁/acd) was found to be slightly anisotropic (a ₀=9.4262(4) Å, K _a =499±4 GPa, K _a ′=19.7±0.9; c ₀=18.6964(6) Å, K _c =657±6 GPa, K _c ′=15.7±1.4) which can be attributed to the fact that the Mn³⁺-O bonds, which are the most compressible bonds, are aligned closer to the (001) plane than to the c axis. The large bulk modulus is the result of the structural topology in which 2/3 and 1/2 of the edges of the Mn²⁺O₈ and Mn³⁺O₆ polyhedra share edges with other polyhedra. The Mn²⁺O₈ polyhedra were found to compress isotropically, whereas anisotropic compressional behaviour was observed for all three Mn³⁺O₆ octahedra. Although the polyhedral geometry of all three crystallographically independent Mn³⁺ sites shows the same type of uniaxially elongated distortion, the compression of the individual octahedral configurations was found to be strongly dependent upon both the geometry of the polyhedron itself and the types of, and the connectivity to, the neighbouring polyhedra. The differences in the configuration of the different oxygen atoms, and therefore the structural topology, is one of the major factors determining the type and degree of the pressure-induced distortion, while the Jahn-Teller effect plays a subordinate role.     

Minimum relative entropy and probabilistic inversion in groundwater hydrology

The similarity between maximum entropy (MaxEnt) and minimum relative entropy (MRE) allows recent advances in probabilistic inversion to obviate some of the shortcomings in the former method. The purpose of this paper is to review and extend the theory and practice of minimum relative entropy. In this regard, we illustrate important philosophies on inversion and the similarly and differences between maximum entropy, minimum relative entropy, classical smallest model (SVD) and Bayesian solutions for inverse problems. MaxEnt is applicable when we are determining a function that can be regarded as a probability distribution. The approach can be extended to the case of the general linear problem and is interpreted as the model which fits all the constraints and is the one model which has the greatest multiplicity or “spreadout” that can be realized in the greatest number of ways. The MRE solution to the inverse problem differs from the maximum entropy viewpoint as noted above. The relative entropy formulation provides the advantage of allowing for non-positive models, a prior bias in the estimated pdf and `hard' bounds if desired. We outline how MRE can be used as a measure of resolution in linear inversion and show that MRE provides us with a method to explore the limits of model space. The Bayesian methodology readily lends itself to the problem of updating prior probabilities based on uncertain field measurements, and whose truth follows from the theorems of total and compound probabilities. In the Bayesian approach information is complete and Bayes' theorem gives a unique posterior pdf. In comparing the results of the classical, MaxEnt, MRE and Bayesian approaches we notice that the approaches produce different results. In␣comparing MaxEnt with MRE for Jayne's die problem we see excellent comparisons between the results. We compare MaxEnt, smallest model and MRE approaches for the density distribution of an equivalent spherically-symmetric earth and for the contaminant plume-source problem. Theoretical comparisons between MRE and Bayesian solutions for the case of the linear model and Gaussian priors may show different results. The Bayesian expected-value solution approaches that of MRE and that of the smallest model as the prior distribution becomes uniform, but the Bayesian maximum aposteriori (MAP) solution may not exist for an underdetermined case with a uniform prior.     

Archaean quartz arenites in the Canadian Shield: examples from the Superior and Churchill Provinces

Units of remarkably pure Archaean quartz arenite occur in the northwestern part of the Superior Province and in the northern terrane of the Western Churchill Province (Rae Province) of the Canadian Shield. In the Superior Province, silica-cemented quartz arenites of Archaean age are well preserved in several greenstone belts. The example from the Keeyask Lake sedimentary assemblage displays tabular–planar and trough cross-beds, ripple marks, reactivation surfaces and pebble lag deposits. In spite of penetrative deformation and greenschist-grade metamorphism, primary textures are extremely well preserved, showing framework grains to be very well rounded and sorted. The succession of Keeyask Lake quartz-arenite beds is overlain by siltstones containing small-scale stratiform, domal and columnar stromatolites. A shallow-marine environment of deposition is inferred. Detrital heavy minerals include pyrite, magnetite, zircon, tourmaline, apatite, sphene and topaz. In the northern part of the Western Churchill Province (Rae Province), Archaean quartz arenites occur in northeasterly trending belts where intense structural deformation has in most places obscured or obliterated primary textures and structures. This has led to speculation that some of these units are metachert or recrystallized vein quartz, but local preservation of primary textures and structures provides clear evidence of epiclastic origin. In the example described herein, quartz arenites of the Woodburn Lake Group display sparse occurrences of trough and tabular–planar cross-beds, channels, ripple marks and pebble lag deposits. Probable environments of deposition for these quartz arenites include fluvial systems and shallow-marine shelf settings. The occurrence of unequivocal quartz-arenite clasts in beds of intercalated conglomerate provides direct evidence of at least two episodes of accumulation of almost pure quartz sand. Thin sections and polished slabs reveal frameworks of clastic quartz grains with little to no matrix (now mainly muscovite), and rare detrital grains of accessory heavy minerals, predominantly zircon and opaque iron oxides. Pyrite and other sulphides have been introduced along fractures, but some intergranular sulphide grains may be of detrital origin. The principal source for the quartz arenites in both areas must have been quartz-rich granitoid rocks. Conditions of intense chemical weathering are indicated. The widespread occurrence of extremely mature quartz arenites throughout Archaean terranes of the Canadian Shield, and in other shields of the world, are suggestive of crustal stability during early Earth history. The association of quartz arenites and ultramafic rocks, uncharacteristic of younger terranes, is now recognized in many Archaean greenstone belts of the Canadian Shield.     

Quaternary and extant euryhaline Lamprothamnium Groves (Charales) from Australia: Gyrogonite morphology and paleolimnological significance

Charophytes are very common in Australian modern and Quaternary waterbodies, and are quite commonly incorrectly reported as “Chara” sp. or Lamprothamnium papulosum (Wallroth) Groves. This paper is the first attempt at the identification of the widespread euryhaline genus Lamprothamnium in Australia, and its use as a paleoenvironmental indicator. Lamprothamnium is distributed worldwide in all continents, except north and central America. The Australian environment, characterized by increasing aridity during the last 500 ka, has an abundance of saline lakes. We sampled 30 modern lakes and identified extant Lamprothamnium macropogon (A. Braun) Ophel and Lamprothamnium succinctum (A. Braun in Ascherson) Wood. Fossil gyrogonites, from lacustrine sediments ∼65 ka old from Madigan Gulf, Lake Eyre, were identified as Lamprothamnium williamsii sp. nov. We applied statistical analysis (analysis of variance, ANOVA) to the morphometry of the gyrogonites from one fossil and three living Lamprothamnium populations. The ANOVA test suggests all the populations are different, including two separate populations of extant L. macropogon, interpreted in this case as the expression of ecophenotypic variability. Lamprothamnium is a useful paleoenvironmental indicator because it indicates a non-marine environment with varying salinity ranging from fresh (usually 2–3 g l⁻¹) to 70 g l⁻¹, and water bodies holding water for at least 70 consecutive days. Collectively, these parameters provide important information in the study of ephemeral habitats.     

Laboratory Column Experiments Using Polymer Mats to Remove Selected VOCs, PAHs, and Pesticides from Ground Water

Large-scale column experiments were undertaken to evaluate the potential of polymer mats to remove selected volatile organic compounds, polycyclic aromatic hydrocarbons, and pesticides (atrazine and fenamiphos) from ground water and potentially to act as permeable reactive barriers in contaminated ground water environments. The polymer mats, composed of interwoven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2 m long flow-through columns. The polymer mats proved efficient in physically removing (stripping) benzene and naphthalene from contaminated water. Removal efficiencies for both these compounds from an aqueous phase flowing past a polymer mat were 75% or greater. However, for atrazine and fenamiphos, removal efficiencies were 5% or less, probably as a result of their lower Henry's law constants and possibly lower polymer diffusion coefficients.
These experiments indicate that, at least for relatively volatile compounds, polymer mats can provide a remediation technique for the removal of organic compounds from contaminated water. Application of this technique may be well suited as a longer-term, semipassive strategy to remediate contaminated ground water, using natural ground water flow to deliver contaminated ground water to polymer mats engineered as sorption-stripping barriers.
Additional benefits of this technique may include targeted delivery of gaseous chemical amendments, such as oxygen, to enhance aerobic biodegradation and to further reduce any residual concentrations of contaminants.     

The effects of a constant volume deformation on the magnetization of an artificial sediment

Anhysteretic remanent magnetization (DC field = 1 Oe, peak AC field = 1000 Oe) was given to an artificial sediment consisting of a kaolinite matrix and a 0.03% magnetic fraction of needle-shaped magnetite grains. The mean grain size of the clay flakes and the magnetite needles was approximately 0.5 μm. This sediment was subjected to plane strain while maintaining constant volume. The axis of maximum compression was shortened by as much as 331/3%, which produced no significant change in the direction of magnetization with a decrease in intensity of 28%. A continuous deformation model, in which the magnetite needles are embedded in a plastically deforming linearly homogeneous medium, failed to explain these results. A discontinuous deformation model was more successful. In this model, deformation occurs mainly in shear zones bounding blocks which translate along the shears. Only those magnetite grains in the shear zones rotate, and from symmetry considerations no net change in the direction of magnetization is predicted. Because magnetite grains rotate in opposite directions in complementary sets of shears, the model predicts a decrease in intensity comparable to that which was observed.     

The UV-Visible Absorption Cross-Sections and Atmospheric Photolysis Rate of HOI

The UV-visible absorption cross-sections of HOI have been recorded over the wavelength range 278-494 nm and at 298 K following generation of HOI in the gas phase using laser flash photolysis. The gas phase reaction of OH with I₂ was used to produce HOI, and the absorption spectrum of HOI was calibrated relative to the consumption of I₂. The HOI spectrum recorded exhibits 2 broad absorption maxima of = 3.99 × 10^-19 cm² and = 2.85 × 10^-19 cm², centred at 338.4 nm and 404.8 nm respectively. The spectrum is adequately described by a parameterisation consisting of two semi-logarithmic Gaussian distribution functions. The HOI spectrum is more intense than that recorded in previous work of Jenkin, but is in good agreement with more recent work by Bauer et al. The parameterised HOI absorption spectrum recorded in this work was used in a radiative model to calculate the atmospheric photolysis rate (J-value) of HOI. These results indicate that, under most sunlit conditions, HOI has a lifetime with respect to solar photolysis of the order of minutes. Experiments attempting to generate HOI by the reaction of O atoms with C₂H₅I led to complex absorption spectra containing a negative contribution to the absorption from the photolytic removal of an unidentified species. In addition, evidence was found for adsorption and desorption of an iodine-containing species in the reaction vessel. This behaviour is rationalised in terms of the disproportionation of HOI to I₂O, and an uncalibrated spectrum tentatively attributed to I₂O has been recorded.     

Photochemical aspects of tropospheric iodine behaviour

The I-atom sensitised decomposition of ozone in air at 1 atm pressure and ambient temperature has been investigated. Iodine atoms were produced by photolysis of I₂ using visible light or of CH₃I using ultraviolet light. In both cases, the quantum yield for O₃ decomposition was 1.25 (±0.11) per I atom. An important role is proposed for the self-reaction of IO radicals leading to higher oxides of iodine, IO+IO(+M)I₂O₂(+M)higher oxides, which predominated over the bimolecular reaction leading to regeneration of I atoms, IO+IO2I+O₂, with k _2a/k _2b4. Simple computer modelling calculations indicate that reaction (2a) may be important in determining the fate of photolabile iodine species in the atmosphere. The consequences for the behaviour of radioiodine releases are also discussed.     

Li,Sr, Mg,and Na in foraminiferal calcite shells from laboratory culture,sediment traps,and sediment cores

Constant-temperature laboratory culture experiments of the planktonic foraminiferal species Globigerinoides sacculifer (Brady) suggest that the ratios of Li and Sr to Ca in the shells are a function of these ratios in the culture solutions. $\text{Mg}\text{Ca}$ and $\text{Na}\text{Ca}$ in the shells did not vary with changes of these ratios in the culture solution. These are the first direct determinations of the relationship between foraminiferal shell chemistry and solution composition.The possibility of temperature dependence for the minor elemental composition of foraminiferal shells was also investigated in the laboratory and by analysis of several planktonic and one benthic foraminiferal species from sediment trap and sediment core samples. The $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios in the natural samples roughly correlate with calcification temperature, whereas differences in the Li/Ca ratios are small and not systematically related to temperature. However, laboratory culture experiments at 20°C and 30°C showed no variation in the $\text{Li}\text{Ca}$, $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios with calcification temperature for the planktonic foraminifera G. sacculifer and Orbulina universa. Therefore, observed differences in the $\text{Sr}\text{Ca}$, $\text{Mg}\text{Ca}$, and $\text{Na}\text{Ca}$ ratios for the sediment trap and core foraminiferal samples cannot be ascribed to direct effects of calcification temperature, but may be due to some other environmental factor which is correlated with temperature.