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

Javiera Cervini-Silva  Benjamin Gilbert  Sirine Fakra  Stephan Friedlich  Jillian Banfield   《Geochimica et cosmochimica acta》2008,72(10):2454-2464

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.  相似文献   

Preliminary Field Studies Using Earth Resistivity Measurements for Delineating Zones of Contaminated Ground Water     

Don L. Warner 《Ground water》1969,7(1):9-16

  相似文献   

The future for ocean technology : by Glyn Ford, Chris Niblett and Lindsay Walker Frances Pinter, London and New Hampshire, 1987, xii + 139 pp, £17.50     

Don Lennard 《Marine Policy》1987,11(4)

  相似文献   

Vertical migration and mortality of benthos in dredged material: Part III—polychaeta     

Don Maurer  Richard T Keck  Jeff C Tinsman  Wayne A Leathem 《Marine environmental research》1982,6(1):49-68

The survival of benthic invertebrates from dredging and disposal activities is a major environmental concern in such projects. The purpose of the research described in this paper was to determine the ability of benthos (polychaetes, Scoloplos fragilis and Nereis succinea) to migrate vertically in natural and exotic sediments and to determine the survival of benthos when exposed to particular amounts of simulated dredged material.Mortalities generally increased with increased sediment depth, exotic sediment and burial time. Temperature also affected vertical migration and mortalities. These experiments, together with other experiments conducted by us and other workers, indicate that polychaetes in particular, and benthos in general, can survive dredging and disposal projects. Under certain conditions several major taxa (polychaetes, molluscs, crustaceans) can be expected to successfully recolonise disposal sites by vertical migration.  相似文献   

Vertical migration and mortality of benthos in dredged material: Part II—crustacea     

Don Maurer  Richard T. Keck  Jeff C. Tinsman  Wayne A. Leathem 《Marine environmental research》1981,5(4):301-317

Benthic invertebrates have many characteristics which make them prime candidates for burial studies in dredged material. A major concern in dredging and disposal projects is the effect of burial on the survival of benthic invertebrates. The purpose of the research reported in this paper was to determine the ability of estuarine benthos—in particular three species of molluscs (Mercenaria mercenaria, Nucula proxima and Ilyanassa obsoleta)—to migrate vertically in natural and exotic sediments and to determine the survival of benthos when exposed to particular amounts of simulated dredged material.Mortalities generally increased with increased sediment depth, with increased burial time and with overlying sediments whose particle size distribution differed from that of the species native sediment. Temperature affected mortalities and vertical migration. It was concluded that vertical migration is a viable process which can significantly affect rehabilitation of a dredged disposal area. Under certain conditions, vertical migration should be considered, together with larval settling and immigration from outside impacted areas, as a mechanism of recruiting a dredgedump site.  相似文献   

Bringing GPS into harsh environments for fully automated deformation monitoring     

Jason Bond  Adam Chrzanowski  Don Kim 《GPS Solutions》2008,12(1):1-11

Engineering projects that require deformation monitoring frequently utilize geodetic sensors to measure displacements of target points located in the deformation zone. In situations where control stations and targets are separated by a kilometer or more, GPS can offer higher precision position updates at more frequent intervals than can normally be achieved using total station technology. For large-scale deformation projects requiring the highest precision, it is therefore advisable to use a combination of the two sensors. In response to the need for high precision, continuous GPS position updates in harsh deformation monitoring environments, a software has been developed that employs triple-differenced carrier-phase measurements in a delayed-state Kalman filter. Two data sets were analyzed to test the capabilities of the software. In the first test, a GPS antenna was displaced using a translation stage to mimic slow deformation. In the second test, data collected at a large open pit mine were processed. It was shown that the delayed-state Kalman filter developed could detect millimeter-level displacements of a GPS antenna. The actual precision attained depends upon the amount of process noise infused at each epoch to accommodate the antenna displacements. Higher process noise values result in quicker detection times, but at the same time increase the noise in the solutions. A slow, 25 mm displacement was detected within 30 min of the full displacement with sigma values in E, N and U of ±10 mm or better. The same displacement could also be detected in less than 5 h with sigma values in E, N and U of ±5 mm or better. The software works best for detecting long period deformations (e.g., 20 mm per day or less) for which sigma values of 1–2 mm are attained in all three solution components. It was also shown that the triple-differenced carrier-phase observation can be used to significantly reduce the effects of residual tropospheric delay that would normally plague double-differenced observations in harsh GPS environments.

Don KimEmail:

  相似文献   

Earth and Venus: A comparative study     

A.E. Ringwood  Don L. Anderson 《Icarus》1977,30(2):243-253

The observed density of Venus is about 2% smaller than would be expected if Venus were a twin planet of the Earth, possessing an identical internal composition and structure. In principle, this could be explained by a process of physical segregation of metal particles from silicate particles in the solar nebula prior to accretion, so that Venus accreted from relatively metal-depleted material. However, this model encounters severe difficulties in explaining the nature of the physical segregation process and also the detailed chemical composition of the Earth's mantle. Two alternative hypotheses are examined, both of which attempt to explain the density difference in terms of chemical fractionation processes. Both of these hypotheses assume that the relative abundances of the major elements Fe, Si, Mg, Al, and Ca are similar in both planets. According to the first hypothesis, a larger proportion of the total iron in Venus is present as iron oxide in the mantle, so that the core-to-mantle ratio is smaller than in the Earth. This model implies that Venus is more oxidized than the Earth, with its lower intrinsic density (i.e., corrected to equivalent pressures and temperatures) due to the larger amount of oxygen present. The difference between oxidation states is attributed to differing degrees of accretional heating arising from the relatively smaller mass of Venus. On the other hand, the second hypothesis maintains that Venus is more reduced than the Earth, with its mantle essentially devoid of oxidized iron. The difference intrinsic densities is attributed to the Earth accreting at a lower temperature than Venus as a result of the Earth's greater distance from the center of the nebula. As a result, large amounts of sulfur accreted on the Earth but not on Venus. The sulfur, which entered the core, is believed to have increased the mean density of the Earth because of its relatively high atomic weight. The hypothesis also implies that most of the Earth's potassium, because of its chalcophile properties, entered the core.These hypotheses are evaluated in the light of existing data. The second hypothesis leads to an intrinsic density for Venus which is only 0.4% smaller than that of the Earth. This difference is much smaller than is believed to exist. A wide range of chemical evidence is found to be unfavorable to this second hypothesis, but to be consistent with the interpretation that Venus is more oxidized than the Earth, as required by the first hypothesis.  相似文献   

Transmission electron microscopy of subsolidus oxidation and weathering of olivine     

Jillian F. Banfield  David R. Veblen  Blair F. Jones 《Contributions to Mineralogy and Petrology》1990,106(1):110-123

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.  相似文献   

Groundwater resources management under environmental constraints in Shiroishi of Saga plain,Japan     

Nguyen Cao Don  Nguyen Thi Minh Hang  Hiroyuki Araki  Hiroyuki Yamanishi  Kenichi Koga 《Environmental Geology》2006,49(8):1223-1223

  相似文献   

Geochemistry and Rb–Sr geochronology of a ductile shear zone in the Orlica-Śnieżnik dome (West Sudetes, Poland)     

Ulrich Lange  Michael Bröcker  Klaus Mezger  Jerzy Don 《International Journal of Earth Sciences》2002,91(6):1005-1016

Amphibolite-facies orthogneisses of the Orlica-vnie™nik dome in the West Sudetes (Poland) show a local continuous transition from weakly deformed augen gneisses to finely laminated mylonites. Field evidence indicates that ductile shearing developed pre- or syntectonically to a migmatization event. Bulk-rock compositions of variably deformed samples yield no indications for deformation- and/or fluid-enhanced element mobility and redistribution. ⁸⁷Rb-⁸⁶Sr geochronology (biotite, phengite, whole rock) places time constraints on the deformation process and the post-orogenic cooling history. Phengite- and biotite-whole-rock pairs yield Rb-Sr ages of 340 to 334 Ma and 335 to 294 Ma, respectively, independent of the degree of deformation. The weighted mean of phengite-whole-rock pairs indicates an age of 337.4DŽ.3 Ma. Combining most of the biotite-whole-rock data yields a weighted mean age of 328.6dž.4 Ma. Because of their different closure temperatures for the Rb-Sr system, these differences are interpreted to date cooling after a thermal event. Direct dating of the deformation is not possible, but the cooling history record defines a minimum age for the development of ductile shearing and the last migmatization event. These time constraints provide evidence for the initiation of crustal collapse during or immediately following peak metamorphic conditions. The results of this study further document the importance of Variscan metamorphism in the Orlica-vnie™nik dome.  相似文献