Formation and stability of schwertmannite in acidic mining lakes

Schwertmannite (ideal formula: Fe₈O₈(OH)₆SO₄) is typically found as a secondary iron mineral in pyrite oxidizing environments. In this study, geochemical constraints upon its formation are established and its role in the geochemical cycling of iron between reducing and oxidizing conditions are discussed. The composition of surface waters was analyzed and sediments characterized by X-ray diffraction, FTIR spectroscopy and determination of the Fe:S ratio in the oxalate extractable fraction from 18 acidic mining lakes. The lakes are exposed to a permanent supply of pyritegenous ferrous iron from adjacent ground water. In 3 of the lakes the suspended matter was fractionated using ultra filtration and analyzed with respect to their mineral composition. In addition, stability experiments with synthetic schwertmannite were performed. The examined lake surface waters were O₂-saturated and have sulfate concentrations (10.3 ± 5.5 mM) and pH values (3.0 ± 0.6) that are characteristic for the stability window of schwertmannite. Geochemical modeling implied that i) the waters were saturated with respect to schwertmannite, which controlled the activity of Fe³⁺ and sulfate, and ii) a redox equilibrium exists between Fe²⁺ and schwertmannite. In the uppermost sediment layers (1 to 5 cm depth), schwertmannite was detectable in 16 lakes—in 5 of them by all three methods. FTIR spectroscopy also proved its occurrence in the colloidal fraction (1-10 kDa) in all of the 3 investigated lake surface waters. The stability of synthetic schwertmannite was examined as a function of pH (2-7) by a 1-yr experiment. The transformation rate into goethite increased with increasing pH. Our study suggests that schwertmannite is the first mineral formed after oxidation and hydrolysis of a slightly acidic (pH 5-6), Fe(II)-SO₄ solution, a process that directly affects the pH of the receiving water. Its occurrence is transient and restricted to environments, such as acidic mining lakes, where the coordination chemistry of Fe³⁺ is controlled by the competition between sulfate and hydroxy ions (i.e. mildly acidic).     

Organization of oscillatory zoning in zircon: analysis, scaling, geochemistry, and model of a zircon from Kipawa, Quebec, Canada

The character of oscillatory zoning within a zircon crystal from the syenite Kipawa Complex, Quebec, varies with scale of observation. Analysis of an scanning electron microscopy (SEM) back-scatter gray-scale traverse at a resolution of one pixel = 2.43 μm revealed 145 zones over 5130 μm, whereas a detailed high-resolution (one pixel = 0.195 μm) section near the crystal rim revealed 225 zones over 795 μm. In order to mathematically characterize the zoning pattern, wavelet, Fourier, and nonlinear analysis techniques were used on profiles of the SEM gray-scale data, and a series constructed was from the zone widths. Results demonstrate that the zircon oscillatory zoning preserves nonlinear and periodic components. Secondary ion mass spectrometry, electron microprobe, and SEM analyses of trace elements show the SEM back-scatter bright zones are enriched in U, Th, and rare earth elements (REE) in comparison to the darker zones. REE patterns are sharply heavy REE enriched and have negative Eu anomalies and prominent positive Ce anomalies. We model the oscillatory zoning, including a measure of its chemical variation, by use of a periodically forced nonlinear system. Results of this data-driven model are quantitatively similar to the natural data. We envisage that the small-scale oscillatory zoning was the result of a nonlinear feedback process wherein the crystal growth modified the adjacent melt, which in turn affected the crystal composition. The large-scale harmonic zones likely reflect changes in the bulk geochemistry of the system from which the zircon grew.     

Partitioning Between Chlorine Reservoir Species Deduced from Observations in the Arctic Winter Stratosphere

Simultaneous observations of several chlorine source gases, as well asHCl and ClO, have been performed in the Arctic stratosphere on 1 and 9February 1994, using balloon-borne instrumentation as a contribution toSESAME (Second European Stratospheric Arctic and Mid latitude Experiment).The observed mixing ratios of HCl and N₂O show a clearanticorrelation. No severe loss of HCl was observed inside the vortex duringour measurement. These measurements showed that during this period at 20 kmand above, HCl was either in excess, or at least as abundant, asClONO₂ and comprised between 50 and 70% of theavailable chlorine, Cl_y. On 1 February, measurements were madeinside the polar vortex. The air mass sampled on this day showed a clearsignature of diabatic descent, and also enhanced levels of ClO with amaximum of 230 pptv at 22.5 km. A 10 day backward trajectory analysis showedthat these air masses had passed a large region of low temperatures a fewhours prior to the measurement. Temperatures along the back trajectory atthe 475 K and 550 K levels (20.1 and 23.7 km respectively) were cold enoughfor heterogeneous chlorine activation to occur, in agreement with theobserved elevated ClO mixing ratios.     

Mechanism and kinetics of the reaction: 1 dolomite + 2 quartz = 1 diopside + 2 CO2: a comparison of rock-sample and of powder experiments

Two experiments using cylindrical samples of a dolomite-quartz rock were carried out in a conventional hydrothermal apparatus for the forward reaction: 1 dolomite + 2 quartz = 1 diopside + 2 CO₂, in order to compare the mechanism and the kinetics with results from experiments using mineral powders of dolomite and quartz at the same P-T-X conditions. Experimental conditions were as follows: total pressure 500 MPa; temperature 680° C (overstepping 65° C); CO₂ content of the fluid phase, consisting of carbon dioxide and water, was nearly 90 mol%; the fluid/rock ratio was 1:37, and the H₂O/rock ratio was about 1:740; run duration was 92 days. Scanning electron microscope (SEM) examination of a polished axial section of the rock cylinders after the run, using back-scattered electrons (BSE), shows that the reaction produced corona textures. The diopside crystals nucleate and grow exclusively on dolomite surfaces adjacent to quartz grains, i.e. in regions where there is intimate contact between the reactants. The dolomite matrix, in contrast, is diopside free. A concept of microsystems is used to compare directly the rock cylinder results with those from runs done with mineral powders. The microsystems, which consist of quartz, dolomite and diopside, are connected by the intergranular space which is filled by the fluid phase. The SEM analysis of the rock cylinders indicates a dissolution-crystallization mechanism operating in the microsystems; this is consistent with the results of experiments using dolomite quartz powders (Lüttge et al. 1989). It can be demonstrated that reaction kinetics in mineral powder runs are interface controlled as long as the newly formed diopside crystals do not cover the dolomite surfaces completely (Lüttge and Metz 1991 c). This result is applicable to each microsystem of the rock cylinder, since the reaction mechanism and the resulting textures are the same in both kinds of experiments. The reaction is much slower outside the microsystems, i.e. in the dolomite matrix but in the close vicinity of the quartz grains. At these places, the reaction is controlled by the transport of Si-species in the CO₂-rich fluid phase filling the intergranular space. The reaction is absent in quartz-free regions of the dolomite matrix. Calculations and measurements of the extent of reaction progress in both kinds of experiments give results of the same order of magnitude: the conversion, and therefore the reaction rate, differs by less than a factor of two. The conclusion is that there are no differences, in principle, concerning mechanisms, rate controls, rates, and resulting textures between rock cylinder experiments, and mineral powder experiments.     

Analytical prediction of the collapse earthquake for R/C buildings: Suggested methodology

Criteria to be used for the analytical prediction of collapse of R/C buildings subjected to earthquake excitation are suggested. It is attempted to include in the criteria as many of the parameters involved as possible, while keeping the complexity, as well as the cost of analysis reasonably low. Two combined collapse criteria are finally suggested, corresponding to member failure and storey failure. Using these criteria, quantitative estimations can be obtained of the actual values of behaviour factors (q-factors) used in modern seismic codes. The ground motion dependence of these factors, as well as the sensitivity of their calculated values to the assumption made about the stiffness of R/C members, is illustrated with reference to two typical structures.     

Using scintillation at two wavelengths to measure path-averaged heat fluxes in free convection

Local free convection scaling is one of the obvious triumphs of boundary-layer similarity theory. In free convection, there is no dynamic velocity scale; the sensible and latent heat fluxes, therefore, scale directly with the temperature and humidity structure parameters C _t ² and C _q ². By using scintillation to measure the refractive index structure parameter C _n ² at two electromagnetic (EM) wavelengths, we can obtain C _t ² and C _q ² and, thus, in effect, measure path-averaged values of the sensible and latent heat fluxes. Here I describe this so-called two-wavelength method for free convection, derive quantitative guidelines for optimizing the method, and evaluate its potential accuracy. I show that the two-wavelength method works best when one EM wavelength is in the visible or infrared region and the other is in the millimeter or radio region. When the Bowen ratio is between -5 and -0.1 or between 0.1 and 5, the expected accuracy of the measured fluxes is ±10–20% — typical of what is possible with eddy-correlation measurements. With the two-wavelength method, however, the fluxes represent spatial averages.     

Enriched back-arc basin basalts from the northern Mariana Trough: implications for the magmatic evolution of back-arc basins

The composition of basalts erupted at the earliest stages in the evolution of a back-arc basin permit unique insights into the composition and structure of the sub-arc mantle. We report major and trace element chemical data and O-, Sr-, Nd-, and Pb- isotopic analyses for basalts recovered from four dredge hauls and one ALVIN dive in the northern Mariana Trough near 22°N. The petrography and major element chemistry of these basalts (MTB-22) are similar to tholeiites from the widest part of the Trough, near 18°N (MTB-18), except that MTB-22 have slightly more K₂O and slightly less TiO₂. The trace element data exhibit a very strong arc signature in MTB-22, including elevated K, Rb, Sr, Ba, and LREE contents; relatively lowK/Ba and highBa/La andSr/Nd. The Sr- and Nd- isotopic data plot in a field displaced from that of MTB-18 towards Mariana arc lavas, and the Pb-isotopic composition of MTB-22 is indistinguishable from Mariana arc lavas and much more homogeneous than MTB-18. Mixing of 50–90% Mariana arc component with a MORB component is hypothesized. We cannot determine whether this resulted from physical mixing of arc mantle and MORB mantle, or whether the arc component is introduced by metasomatism of MORB-like mantle by fluids released from the subducted lithosphere. The strong arc signature in back-arc melts from the Mariana Trough at 22°N, where the back-arc basin is narrow, supports general models for back-arc basin evolution whereby early back-arc basin basalts have a strong arc component which diminishes in importance relative to MORB as the back-arc basin widens.     

A new telluric KCl probe using Filloux's AgAgCl electrode

The measurement of the telluric field's long-time variations requires stable instruments in the period range above 1 day. Obviously, most problems arise from drifting voltages between the telluric probes. Good results have been achieved using a three chamber Hempfling KCl probe together with Filloux's AgAgCl electrode. However, a one chamber probe of 0.6 m length and 0.06 m diameter filled with saturated KCl solution may be sufficient for some applications and additionally allows permanent control of the electrolyte's salt concentration. In a field test the telluric field at a single site was simultaneously observed using one and three chamber probes separated by 25 and 55 m resp. For periods shorter than 1 hour the noise level of the electrodes was found to be less than 1 (mV)²/Hz whereas in the period range between 1 hour and 1 day it increases to 100 (mV)²/Hz. Consequently, surveys investigating long periods of the telluric field can be carried out using small electrode separations of a few tens of meters. Furthermore, the stability of this probe negates the need to interrupt the time series for servicing of the probe. However, the one chamber probe is somewhat inferior to the three chamber probe with regard to temperature dependence at long periods.