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   

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   

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

Gregory K. Druschel  Robert J. Hamers  George W. Luther III  Jillian F. Banfield 《Aquatic Geochemistry》2003,9(2):145-164

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.  相似文献   

Kinetics of the Gas-Phase Reactions of OH Radicals, NO3 Radicals and O3 with Three C7-Carbonyls Formed From The Atmospheric Reactions of Myrcene, Ocimene and Terpinolene     

Jillian Baker  Janet Arey  Roger Atkinson 《Journal of Atmospheric Chemistry》2004,48(3):241-260

Rate constants for the gas-phase reactions of OH radicals, NO₃ radicals and O₃ with the C₇-carbonyl compounds 4-methylenehex-5-enal [CH₂=CHC(=CH₂)CH₂CH₂CHO], (3Z)- and (3E)-4-methylhexa-3,5-dienal [CH₂=CHC(CH₃)=CHCH₂CHO] and 4-methylcyclohex-3-en-1-one, which are products of the atmospheric degradations of myrcene, Z- and E-ocimene and terpinolene, respectively, have been measured at 296 ± 2 K and atmospheric pressure of air using relative rate methods. The rate constants obtained (in cm³ molecule^–1 s^–1 units) were: for 4-methylenehex-5-enal, (1.55 ± 0.15) × 10^–10, (4.75 ± 0.35) × 10^–13 and (1.46 ± 0.12) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3Z)-4-methylhexa-3,5-dienal: (1.61 ± 0.35) × 10^–10, (2.17 ± 0.30) × 10^–12, and (4.13 ± 0.81) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; for (3E)-4-methylhexa-3,5-dienal: (2.52 ± 0.65) × 10^–10, (1.75 ± 0.27) × 10^–12, and (5.36 ± 0.28) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively; and for 4-methylcyclohex-3-en-1-one: (1.10 ± 0.19) × 10^–10, (1.81 ± 0.35) × 10^–12, and (6.98 ± 0.40) × 10^–17 for the OH radical, NO₃ radical and O₃ reactions, respectively. These carbonyl compounds are all reactive in the troposphere, with daytime reaction with the OH radical and nighttime reaction with the NO₃ radical being predicted to dominate as loss processes and with estimated lifetimes of about an hour or less.  相似文献   

The surface of labradorite feldspar after acid hydrolysis     

William H. Casey  Henry R. Westrich  Thomas Massis  Jillian F. Banfield  George W. Arnold 《Chemical Geology》1989,78(3-4):205-218

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.  相似文献   

Buruanga peninsula and Antique Range: Two contrasting terranes in Northwest Panay,Philippines featuring an arc–continent collision zone     

Lawrence R. Zamoras  Mary Grace A. Montes  Karlo L. Queaño  Edanjarlo J. Marquez  Carla B. Dimalanta  Jillian Aira S. Gabo  Graciano P. Yumul Jr. 《Island Arc》2008,17(4):443-457

Alternating chert–clastic sequences juxtaposed with limestone blocks, which are units typical of accretionary complexes, constitute the Buruanga peninsula. New lithostratigraphic units are proposed in this study: the Unidos Formation (Jurassic chert sequence), the Saboncogon Formation (Jurassic siliceous mudstone–terrigenous mudstone and quartz‐rich sandstone), the Gibon Formation (Jurassic(?) bedded pelagic limestone), the Libertad Metamorphics (Jurassic–Cretaceous slate, phyllite, and schist) and the Buruanga Formation (Pliocene–Pleistocene reefal limestone). The first three sedimentary sequences in the Buruanga peninsula show close affinity with the ocean plate stratigraphy of the North Palawan terrane in Busuanga Island: Lower–Middle Jurassic chert sequences overlain by Middle–Upper Jurassic clastics, juxtaposed with pelagic limestone. Moreover, the JR5–JR6 (Callovian to Oxfordian) siliceous mudstone of the Saboncogon Formation in the Buruanga peninsula correlates with the JR5–JR6 siliceous mudstone of the Guinlo Formation in the Middle Busuanga Belt. These findings suggest that the Buruanga peninsula may be part of the North Palawan terrane. The rocks of the Buruanga peninsula completely differ from the Middle Miocene basaltic to andesitic pyroclastic and lava flow deposits with reefal limestone and arkosic sandstone of the Antique Range. Thus, the previously suggested boundary between the Palawan microcontinental block and the Philippine Mobile Belt in the central Philippines, which is the suture zone between the Buruanga peninsula and the Antique Range, is confirmed. This boundary is similarly considered as the collision zone between them.  相似文献   

A laser probe Ar/Ar and INAA investigation of four Apollo granulitic breccias     

Jillian A. Hudgins  John G. Spray  Randy L. Korotev 《Geochimica et cosmochimica acta》2008,72(23):5781-5798

Infrared laser probe ⁴⁰Ar/³⁹Ar geochronology, instrumental neutron activation analysis (INAA) and analytical electron microscopy have been performed on four 0.5 × 1.0 × 0.3 cm polished rock tiles of Apollo 16 and 17 granulitic breccias (60035, 77017, 78155, and 79215). Pyroxene thermometry indicates that these samples were re-equilibrated and underwent peak metamorphic sub-solidus recrystallization at 1000-1100 °C, which resulted in homogeneous mineral compositions and granoblastic textures.⁴⁰Ar/³⁹Ar data from this study reveal that three samples (60035, 77017, and 78155) have peak metamorphic ages of ∼4.1 Ga. Sample 79215 has a peak metamorphic age of 3.9 Ga, which may be related to Serenitatis basin formation. All four samples contain moderately high concentrations of meteoritic siderophiles. Enhanced siderophile contents in three of the samples provide evidence for projectile contamination of their target lithologies occurring prior to peak metamorphism.Post-peak metamorphism, low-temperature (<300 °C) events caused the partial resetting of argon in the two finer-grained granulites (60035 and 77017). These later events did not alter the mineralogy or texture of the rocks, but caused minor brecciation and the partial release of argon from plagioclase. Interpretation of the low-temperature data indicates partial resetting of the argon systematics to as young as 3.2 Ga for 60035 and 2.3 Ga for 77017. Cosmic ray exposure ages range from 6.4 to ∼339 Ma.Our results increase the amount of high-precision data available for the granulitic breccias and lunar highlands crustal samples. The results demonstrate the survival of pre-Nectarian material on the lunar surface and document the effects of contact metamorphic and impact processes during the pre-Nectarian Epoch, as well as the low-temperature partial resetting of ages by smaller impact events after 3.9 Ga.The mineralogy and chemical composition of these rocks, as well as exhumation constraints, indicate that the source of heat for metamorphism was within kilometers of the surface via burial beneath impact-melt sheets or hot ejecta blankets.  相似文献   

Geochemistry of the Batang Group in the Zhaokalong Area,Yushu, Qinghai: Implications for the Late Triassic Tectonism in the Northern Sanjiang Region,China   总被引：1，自引：0，他引：1  

LI Huan  XI Xiaoshuang  SUN Huashan  KONG Hu  WU Qianhong  WU Chengming  Jillian Aira S. GABO-RATIO 《《地质学报》英文版》2016,90(2):704-721

The Batang Group in the Zhaokalong area not only hosts an important Fe-Cu polymetallic deposit but also reveal important insights for the Late Triassic tectonism in the northern Sanjiang region. In order to delineate the tectonic setting and evolutionary process of the paleo arc-basin system, geochemical studies on the Batang Group strata have been carried out. The results suggest that andesite in the Zhaokalong area mainly belongs to the tholeiite series and is characterized by obvious fractionation of LREE and HREE, enrichment in LILE and depletion in HFSE, and a distinctly elevated δ~(34)SCDT average of 10.5‰. The sandstone is classified as lithic sandstone, which is also characterized by obvious fractionation of LREE and HREE, as well as weak negative Ce and Eu anomalies. The limestone displays positive Eu anomalies, with δ~(13)CPDB ranging from-1.3‰ to 4.4‰ and δ~(18) OSMOW ranging from 14.6‰ to 22.5‰. These results indicate that the andesite has a dual signature of both arc andesite and rift volcanic rocks, whereas the sandstone may be formed in an active continental margin, and the limestone could be deposited in a weak oxidizing shallow sea. The sandstone in the Zhaokalong area represents sedimentation in a platform slope facies, corresponding to the main stage of the Jinshajing oceanic basin subduction during the middle period of Late Triassic. The continental arc volcanic activity resulted from subsequent strengthened subduction, forming the andesite in the North Qiangtang backarc basin. Afterwards, the limestone was formed after the cessation of magmatic activity. The information gleaned from the Batang Group strata helped constrain the evolution of the paleo-Jomda island arc and Jinshajiang oceanic subduction in the Late Triassic.  相似文献   

The reaction history of kyanite in high‐P aluminous granulites          下载免费PDF全文

Jillian Kendrick  Aphrodite Indares 《Journal of Metamorphic Geology》2018,36(2):125-146

Cathodoluminescence (CL) mapping of kyanite in high pressure, aluminous granulites from the central Grenville Province reveals internal structures that are linked to their metamorphic reaction history. In two samples, individual kyanite crystals are shown to be composite porphyroblasts comprising three distinct generations, defined by their CL intensity and Cr (±V, Ti, Fe and Ga) content, and each separated by resorbed interfaces. In contrast, a sub‐aluminous sample contains two types of kyanite, one as resorbed inclusions in garnet and another in the groundmass or replacing garnet. These textural variants of kyanite are interpreted within the framework of phase equilibria modelling. In P–T pseudosections, a first generation of kyanite, which is only present in the most aluminous samples, is potentially linked to staurolite breakdown, and its resorption is consistent with a subsequent increase in pressure. This kyanite represents the earliest remnant of prograde metamorphism identifiable in these rocks. The second generation, present in the porphyroblasts in the same samples and as inclusions in garnet in the sub‐aluminous sample, is interpreted to be the peritectic product of muscovite dehydration melting. Resorption of this kyanite is consistent with subsequent continuous dehydration melting of biotite, which is also inferred based on microstructural considerations. The final generation of kyanite, present as rims on the prograde kyanite porphyroblasts in aluminous samples and as part of the groundmass or replacing garnet in the sub‐aluminous rock, is interpreted to have grown during melt crystallization upon retrogression. The presence of retrograde kyanite implies that the melt crystallized over a wide range of temperatures, and provides an important constraint on the P–T conditions of the metamorphic peak and on the retrograde P–T path. CL mapping is crucial for identifying retrograde kyanite in aluminous samples, as it preferentially overgrows existing kyanite rather than replacing other prograde phases. The scarcity of kyanite in sub‐aluminous rocks allows retrograde kyanite to grow as discrete crystals that can be identified by optical microscopy. This work attests to the potential of unconventional tools such as CL imaging for deciphering the metamorphic history of rocks.  相似文献   

The use of new economic decision support tools for adaptation assessment: A review of methods and applications,towards guidance on applicability     

Paul Watkiss  Alistair Hunt  William Blyth  Jillian Dyszynski 《Climatic change》2015,132(3):401-416

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