Transmission electron microscopy of subsolidus oxidation and weathering of olivine

Olivine crystals in basaltic andesites which crop out in the Abert Rim, south-central Oregon have been studied by high-resolution and analytical transmission electron microscopy. The observations reveal three distinct assemblages of alteration products that seem to correspond to three episodes of olivine oxidation. The olivine crystals contain rare, dense arrays of coherently intergrown Ti-free magnetite and inclusions of a phase inferred to be amorphous silica. We interpret this first assemblage to be the product of an early subsolidus oxidation event in the lava. The second olivine alteration assemblage contains complex ordered intergrowths on (001) of forsterite-rich olivine and laihunite (distorted olivine structure with Fe³⁺ charge balanced by vacancies). Based on experimental results for laihunite synthesis (Kondoh et al. 1985), these intergrowths probably formed by olivine oxidation between 400 and 800°C. The third episode of alteration involves the destruction of olivine by low-temperature hydrothermal alteration and weathering. Elongate etch-pits and channels in the margins of fresh olivine crystals contain semi-oriented bands of smectite. Olivine weathers to smectite and hematite, and subsequently to arrays of oriented hematite crystals. The textures resemble those reported by Eggleton (1984) and Smith et al. (1987). We find no evidence for a metastable phase intermediate between olivine and smectite (M — Eggleton 1984). The presence of laihunite exerts a strong control on the geometry of olivine weathering. Single laihunite layers and laihunite-forsteritic olivine intergrowths increase the resistance of crystals to weathering. Preferential development of channels between laihunite layers occurs where growth of laihunite produced compositional variations in olivine, rather than where coherency-strain is associated with laihunite-olivine interfaces.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

The surface of labradorite feldspar after acid hydrolysis

After reaction with a pH < 4, the surface of labradorite is extensively enriched in Si and H, and depleted in Al, Ca and Na relative to an unreacted crystal. However, the amount of hydrogen measured in the reacted surface is less than that predicted on the basis of exchange of hydrogen (or hydronium) ions for cations in the feldspar. By analogy with studies of silicate glass, this low concentration of hydrogen suggests that some silanol groups in the reacted surface repolymerize subsequent to ion-exchange and depolymerization reactions. The net result is a relatively porous, Si-rich leached layer which is amorphous to electron diffraction, and which allows rapid diffusion of unreactive solutes.

Both the surface area of the reacted feldspar and the porosity increase with acid hydrolysis. Modeling of nitrogen sorption onto the surface suggests that the pores have a nominal radius of 20–80 Å or less. This distribution of pore sizes resembles other acid-reacted silicate materials, such as glass, chrysotile and kaolinite. Although the mineral surface clearly becomes more porous during acid hydrolysis, the increase in powder area also does not coincide with an increase in the flux of dissolved Si from the powder. We thus attribute most of this increase in area to spallation of the silica-rich surface from the feldspar upon drying.     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Spatial variation of nutrients and primary productivity in the Rufiji Delta mangroves,Tanzania

Determinations of spatial and temporal variations in organic matter and nutrient dynamics in water and sediments are crucial for understanding changes in aquatic bodies. In this study, we (i) determine the spatial dynamics of dissolved inorganic nutrients, during the transition from the dry to the rainy season, and (ii) provide future productivity predictions for the Rufiji Delta mangroves, Tanzania, based on the input of various nutrients. Water samples were collected from six locations, three times per year between April 2012 and January 2014, and analysed for dissolved nutrients, total organic and inorganic carbon, chlorophyll a, chlorophyll b and total carotenoids. The prediction of future net primary productivity in the Rufiji mangroves was undertaken using the software STELLA. The mean nutrient concentrations were of the order: nitrate > phosphate > ammonium > silica > dissolved organic carbon. The study revealed that high nutrient concentrations occurred in the northern part of the Rufiji Delta as a result of anthropogenic influence in the watershed. Modelling of nutrient inputs into the delta indicated enhanced primary productivity, which is expected to increase the vulnerability of water quality in the near future due to eutrophication.     

Evaluation of fibre rope properties for offshore mooring

An examination has been conducted of fibre rope mechanical properties measured in laboratory tests on materials, constructions and terminations intended for deepwater mooring applications. This data, combined with field experience, provide a better understanding of rope behaviour and enhances the knowledge required to engineer fibre ropes for these demanding applications.This has also led to improved laboratory test techniques for measurement of mechanical properties relevant to mooring system response analyses required to meet regulatory requirements. Preliminary evaluation of the data also indicates that a post-test evaluation method to determine retained properties of insert strops removed from mooring lines may be possible.     

湖北铜绿山矿床石英闪长岩的矿物学及Sr-Nd-Pb同位素特征

铜绿山是长江中下游鄂东南矿集区最重要的、大型夕卡岩型Cu-Fe(Au)矿床。本文对该矿区中与成矿密切的石英闪长岩进行了详细的矿物成分、地球化学及Sr-Nd-Pb同位素研究。结果表明:岩石中斜长石主要为更长石(An=21～31);角闪石贫Ti(0.2),高Mg/(Mg+Fe)(0.5),属于富镁角闪石;而黑云母为镁质黑云母。岩石的地球化学具有高硅(58.86%～67.71%),富碱(Na2O+K2O=5.67%～9.63%),富集轻稀土元素(LREE)和大离子亲石元素(LILE),并强亏损元素Nb、Ta、Ti等特征。岩石的(87Sr/86Sr)i为0.7055～0.7069,εNd(t)为-7.65～-3.44;(206Pb/204Pb)i=17.66～18.00,(207Pb/204Pb)i=15.49～15.56,(208Pb/204Pb)i=37.73～38.19。矿物成分、地球化学和同位素特征说明,铜绿山岩体与阳新岩体为同源岩浆的产物,源区为深度大于40km的富集地幔,经下地壳的混染及分离结晶作用形成。岩浆熔体形成的温度应大于889℃。角闪石和黑云母的温度计估算岩浆结晶温度分别为650～800℃和500～630℃,黑云母开始结晶温度略低于角闪石结晶结束温度,压力为1.49kbar,对应侵位深度约4.9km。岩浆具有利于Cu、Fe、Au等成矿元素进入熔体的条件,可能与板块俯冲作用相关。     

Velocity and vorticity measurements of Jupiter's Great Red Spot using automated cloud feature tracking

We have produced mosaics of the Great Red Spot (GRS) using images taken by the Galileo spacecraft in May 2000, and have measured the winds of the GRS using an automated algorithm that does not require manual cloud tracking. Our technique yields a high-density, regular grid of wind velocity vectors that is advantageous over a limited number of scattered wind vectors that result from manual cloud tracking. The high-velocity collar of the GRS is clearly seen from our velocity vector map, and highest wind velocities are measured to be around 170 m s⁻¹. The high resolution of the mosaics has also enabled us to map turbulent eddies inside the chaotic central region of the GRS, similar to those mapped by Sada et al. [Sada, P.V., Beebe, R.F., Conrath, B.J., 1996. Icarus 119, 311-335]. Using the wind velocity measurements, we computed particle trajectories around the GRS as well as maps of relative and absolute vorticities. We have discovered a narrow ring of cyclonic vorticity that surrounds the main anti-cyclonic high-velocity collar. This narrow ring appears to correspond to a ring surrounding the GRS that is bright in 5 μm [Terrile, R.J., Beebe, R.F., 1979. Science 204, 948-951]. It appears that this cyclonic ring is not a transient feature of the GRS, as we have discovered it in a re-analysis of Galileo data taken in 1996 first analyzed by Vasavada et al. [Vasavada, A.R., and 13 colleagues, 1998. Icarus 135, 265-275]. We also calculate how absolute vorticity changes as a function of latitude along a trajectory around the GRS and compare these measurements to similar ones performed by Dowling and Ingersoll [Dowling, T.E., Ingersoll, A.P., 1988. J. Atmos. Sci. 45, 1380-1396] using Voyager data. We show no dramatic evolution in the structure of the GRS since the Voyager era except for additional evidence for a counter-rotating GRS core, an increase in velocity in the main velocity collar, and an overall decrease in the length of the GRS.