The replacement of anthophyllite by jimthompsonite: a model for hydration reactions in biopyriboles

Anthophyllite crystals found in ultramafic lenses of the Lepontine Alps (Switzerland) contain coherent, submicroscopic intergrowths of ordered and disordered biopyribole polysomes. The chain width distributions of disordered polysomes were analyzed using high resolution transmission electron microscopy (HRTEM). Chains wider than triple were interpreted as intermediate products in the transformation of anthophyllite to the triple chain silicate jimthompsonite. The concentration of individual chain types is strongly correlated with the reaction progress. Based on observed zipper terminations and the transformation rules given by Veblen and Buseck (1980) a scheme of possible reaction paths leading from anthophyllite to jimthomp sonite is proposed. The reaction scheme and a simple kinetic model for elementary reactions allow modeling of the observed chain width distributions. The model suggests that the complex reaction paths involving steps with increasing and decreasing chain width are more important in the formation of jimthompsonite than the direct transformation from anthophyllite. The wide chains (>triple) occurring as intermediate products of the multi-step paths are structurally closer to talc than jimthompsonite. The back-transformation of these wide chains to triple chains is, therefore, a strong argument that jimthompsonite is a stable phase and not only a metastable intermediate product in the transformation of anthophyllite to talc. Received: 8 July 1996 / Accepted: 13 December 1996     

Bathymetric and geochemical investigation of Kawah Ijen Crater Lake, East Java, Indonesia

A bathymetric survey of Kawah Ijen crater lake was conducted by acoustic sounding in 1996 to compare the lake morphology with those measured in 1922, 1925 and 1938, and to calculate the present lake volume. Even though the lake experienced several hydrothermal eruptions, the maximum depth became shallower (182 m) than before (200 m), resulting in a reduced lake volume (3.0×10⁷ m³).Fifty-two major and minor constituents including rare earth elements and polythionates (PT) of the lake waters at various depths were determined by ICP-AES, ICP-MS and HPLC, respectively. These ions except for several volatile elements are taken up by lake fringe through congruent dissolution of pyroclastics of Kawah Ijen volcano. Most ions are homogeneously distributed throughout the lake, although PT showed a considerable vertical variation. Rare earth elements (REE) in the Kawah Ijen water as well as those from other hyper-acidic crater lakes show distribution patterns likely due to the three rock dissolution (preferential, congruent and residual) types, and their logarithmic concentrations linearly depend upon the pH values of the lake waters.Using the PT degradation kinetics data, production rates of PT, injection rates of SO₂ and H₂S into the lake were estimated to be 114, 86 and 30 tons/day, respectively. Also travel time of the spring water at the Banyupahit Riverhead from Kawah Ijen was estimated to be 600–1000 days through the consideration of decreasing rates of PT. Molten sulfur stocks containing Sn, Cu, Bi sulfides and Pb-barite exposed on the inner crater slope were presumed to be extinct molten sulfur pools at the former lake bottom. This was strongly supported by the barite precipitation temperature estimated through the consideration of the temperature dependence of Pb-chlorocomplex formation.     

Multicomponent ionic diffusion in porewaters: Coulombic effects revisited

The diffusion of an ion in porewaters cannot occur independently of the other ions in solution as a result of Coulombic coupling, as well as from other effects not considered here. Unfortunately, a longstanding disagreement exists about the correct form and meaning of the equations that describe Coulombic coupling in porewaters, i.e., Ben-Yaakov [Am. J. Sci. 281 (1981) 974] vs. Lasaga [Am. J. Sci. 281 (1981) 981]. This paper re-examines this controversy by reformulating the problem starting from fundamental concepts of mass and charge conservation. We show that these antagonistic formulations are both valid and, in fact, equivalent, when the different interpretations of charge balance are resolved. Most of the disagreements between Ben-Yaakov and Lasaga are then shown to result from differing methods of solution, not fundamental disparities in their models. We note, however, that the explanation for the concept of “stationary” gradients of nonreacting ions as given Ben-Yaakov is inaccurate, and such gradients do lead to diffusive fluxes that are counterbalanced by electrochemical migrational fluxes to produce no net flux (excluding advective flux). We further find that the bicarbonate diffusive flux will not balance the diffusional charge flux of sulfate during its reduction if advection is present. This latter imbalance generates compensating fluxes in the other nonreacting ions. We have applied our theory to a simplified case of sulfate reduction in a marine sediment. The results show that nonreacting ions do diffuse and that with normally expected values of porewater advection, the ratio of the bicarbonate to the sulfate flux can be far different than the ideal value of −2.     

Fitting the Linear Model of Coregionalization by Generalized Least Squares

In geostatistical studies, the fitting of the linear model of coregionalization (LMC) to direct and cross experimental semivariograms is usually performed with a weighted least-squares (WLS) procedure based on the number of pairs of observations at each lag. So far, no study has investigated the efficiency of other least-squares procedures, such as ordinary least squares (OLS), generalized least squares (GLS), and WLS with other weighing functions, in the context of the LMC. In this article, we compare the statistical properties of the sill estimators obtained with eight least-squares procedures for fitting the LMC: OLS, four WLS, and three GLS. The WLS procedures are based on approximations of the variance of semivariogram estimates at each distance lag. The GLS procedures use a variance–covariance matrix of semivariogram estimates that is (i) estimated using the fourth-order moments with sill estimates (GLS₁), (ii) calculated using the fourth-order moments with the theoretical sills (GLS₂), and (iii) based on an approximation using the correlation between semivariogram estimates in the case of spatial independence of the observations (GLS₃). The current algorithm for fitting the LMC by WLS while ensuring the positive semidefiniteness of sill matrix estimates is modified to include any least-squares procedure. A Monte Carlo study is performed for 16 scenarios corresponding to different combinations of the number of variables, number of spatial structures, values of ranges, and scale dependence of the correlations among variables. Simulation results show that the mean square error is accounted for mostly by the variance of the sill estimators instead of their squared bias. Overall, the estimated GLS₁ and theoretical GLS₂ are the most efficient, followed by the WLS procedure that is based on the number of pairs of observations and the average distance at each lag. On that basis, GLS₁ can be recommended for future studies using the LMC.     

Turbulent flow over a dune: Green River,Colorado

Detailed echo‐sounder and acoustic Doppler velocimeter measurements are used to assess the temporal and spatial structure of turbulent flow over a mobile dune in a wide, low‐gradient, alluvial reach of the Green River. Based on the geometric position of the sensor over the bedforms, measurements were taken in the wake, in transitional flow at the bedform crest, and in the internal boundary layer. Spatial distributions of Reynolds shear stress, turbulent kinetic energy, turbulence intensity, and correlation coefficient are qualitatively consistent with those over fixed, two‐dimensional bedforms in laboratory flows. Spectral and cospectral analysis demonstrates that energy levels in the lee of the crest (i.e. wake) are two to four times greater than over the crest itself, with minima over the stoss slope (within the developing internal boundary layer). The frequency structure in the wake is sharply defined with single, dominant peaks. Peak and total spectral and cross‐spectral energies vary over the bedform in a manner consistent with wave‐like perturbations that ‘break’ or ‘roll up’ into vortices that amalgamate, grow in size, and eventually diffuse as they are advected downstream. Fluid oscillations in the lee of the dune demonstrate Strouhal similarity between laboratory and field environments, and correspondence between the peak frequencies of these oscillations and the periodicity of surface boils was observed in the field. Copyright © 2005 John Wiley & Sons, Ltd.     

Morphological and microtectonic analysis of Quaternary deformation from Puná and Santa Clara Islands, Gulf of Guayaquil, Ecuador (South America)

This paper presents the neotectonic study of Santa Clara and Puná Islands sited in the Gulf of Guayaquil eastern part. Both islands are located on the south-western segment of the fault zone bounding to the east the North Andean Block. Fault motion and morphostructural analysis were carried out from Pleistocene age terrain. A two step deformation characterises the South Puná tectonics. The first step involves the Zambapala Cordillera uplift that post-dates Pleistocene sediments and pre-dates a marine terrace correlated with the M.I.S. 11 or 13 (440–550 ka). The second step is the formation of a pull-apart that shows evidence of 2.9 km dextral offset since the M.I.S. 11 or 13, giving an offset mean rate of 5.3 to 6.6 mm/yr. This rate is higher than the one calculated on the Pallatanga Fault northeast of the study area, in the Western Andean Cordillera, suggesting that deformation is split in different fault segments from the Gulf of Guayaquil to the continent. The Zambapala Cordillera uplift and transpression deformation requires a compressive event that may have been induced by the subduction process during the early Pleistocene.     

The Okavango giant mafic dyke swarm (NE Botswana): its structural significance within the Karoo Large Igneous Province

The structural organization of a giant mafic dyke swarm, the Okavango complex, in the northern Karoo Large Igneous Province (LIP) of NE Botswana is detailed. This N110°E-oriented dyke swarm extends for 1500 km with a maximum width of 100 km through Archaean basement terranes and Permo-Jurassic sedimentary sequences. The cornerstone of the study is the quantitative analysis of N>170 (exposed) and N>420 (detected by ground magnetics) dykes evidenced on a ca. 80-km-long section lying in crystalline host-rocks, at high-angle to the densest zone of the swarm (Shashe area). Individual dykes are generally sub-vertical and parallel to the entire swarm. Statistical analysis of width data indicates anomalous dyke frequency (few data <5.0 m) and mean dyke thickness (high value of 17 m) with respect to values classically obtained from other giant swarms. Variations of mean dyke thicknesses from 17 (N110°E swarm) to 27 m (adjoining and coeval N70°E giant swarm) are assigned to the conditions hosting fracture networks dilated as either shear or pure extensional structures, respectively, in response to an inferred NNW–SSE extension. Both fracture patterns are regarded as inherited brittle basement fabrics associated with a previous (Proterozoic) dyking event. The Okavango N110°E dyke swarm is thus a polyphase intrusive system in which total dilation caused by Karoo dykes (estimated frequency of 87%) is 12.2% (6315 m of cumulative dyke width) throughout the 52-km-long projected Shashe section. Assuming that Karoo mafic dyke swarms in NE Botswana follow inherited Proterozoic fractures, as similarly applied for most of the nearly synchronous giant dyke complexes converging towards the Nuanetsi area, leads us to consider that the resulting triple junction-like dyke/fracture pattern is not a definitive proof for a deep mantle plume in the Karoo LIP.     

Quantum-thermodynamic treatment of intrinsic anharmonicity; Wallace’s theorem revisited

Wallace (in Thermodynamics of crystals, 1972) developed a theorem, rooted in rigid lattice dynamics, which incorporates intrinsic anharmonic effects in solids. The practical application of this theorem in mineral physics is computationally involved and this is the main reason for the theorem not getting the attention it deserves. Because intrinsic anharmonicity is an important issue at the extreme conditions in planetary mantles, we derived a method which removes the computational obstacles in applying this theorem. We extended the theorem to incorporate details of the phonon spectrum and tested our algorithm on forsterite (Mg₂SiO₄). Using a least squares inversion technique applied to all available experimental data, we show that it results in an accurate representation of thermodynamic properties and sound wave velocities of Mg₂SiO₄ in its complete pressure–temperature stability range. We also show that the accuracy of our results is not significantly affected by the use of a different equation of state.