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D.R. Veblen

Publications and source records attributed to D.R. Veblen.

5 recordsLinked to original sources

Newly recognized hosts for uranium in the Hanford Site vadose zone

Uranium contaminated sediments from the U.S. Department of Energy’s Hanford Site have been investigated using electron microscopy. Six classes of solid hosts for uranium were identified. Preliminary sediment characterization was carried out using optical petrography, and electron microprobe analysis (EMPA) was used to locate materials that host uranium. All of the hosts are fine-grained and intergrown with other materials at spatial scales smaller than the analytical volume of the electron microprobe. A focused ion beam (FIB) was used to prepare electron-transparent specimens of each host for the transmission electron microscope (TEM). The hosts were identified as: (1) metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 ·8H 2 O]; (2) coatings on sediment clasts comprised mainly of phyllosilicates; (3) an amorphous zirconium (oxyhydr)oxide found in clast coatings; (4) amorphous and poorly crystalline materials that line voids within basalt lithic fragments; (5) amorphous palagonite surrounding fragments of basaltic glass; and (6) Fe- and Mn-oxides. These findings demonstrate the effectiveness of combining EMPA, FIB, and TEM to identify solid-phase contaminant hosts. Furthermore, they highlight the complexity of U geochemistry in the Hanford vadose zone, and illustrate the importance of microscopic transport in controlling the fate of contaminant metals in the environment.

Geochimica et Cosmochimica Acta↗

Naturally weathered feldspar surfaces in the Navajo Sandstone aquifer, Black Mesa, Arizona: Electron microscopic characterization

Naturally weathered feldspar surfaces in the Jurassic Navajo Sandstone at Black Mesa, Arizona, was characterized with high-resolution transmission and analytical electron microscope (HRTEM-AEM) and field emission gun scanning electron microscope (FEG-SEM). Here, we report the first HRTEM observation of a 10-nm thick amorphous layer on naturally weathered K-feldspar in currently slightly alkaline groundwater. The amorphous layer is probably deficient in K and enriched in Si. In addition to the amorphous layer, the feldspar surfaces are also partially coated with tightly adhered kaolin platelets. Outside of the kaolin coatings, feldspar grains are covered with a continuous 3-5 ??m thick layer of authigenic smectite, which also coats quartz and other sediment grains. Authigenic K-feldspar overgrowth and etch pits were also found on feldspar grains. These characteristics of the aged feldspar surfaces accentuate the differences in reactivity between the freshly ground feldspar powders used in laboratory experiments and feldspar grains in natural systems, and may partially contribute to the commonly observed apparent laboratory-field dissolution rate discrepancy. At Black Mesa, feldspars in the Navajo Sandstone are dissolving at ???105 times slower than laboratory rate at comparable temperature and pH under far from equilibrium condition. The tightly adhered kaolin platelets reduce the feldspar reactive surface area, and the authigenic K-feldspar overgrowth reduces the feldspar reactivity. However, the continuous smectite coating layer does not appear to constitute a diffusion barrier. The exact role of the amorphous layer on feldspar dissolution kinetics depends on the origin of the layer (leached layer versus re-precipitated silica), which is uncertain at present. However, the nanometer thin layer can be detected only with HRTEM, and thus our study raises the possibility of its wide occurrence in geological systems. Rate laws and proposed mechanisms should consider the possibility of this amorphous layer on feldspar surface. ?? 2006 Elsevier Inc. All rights reserved.

Geochimica et Cosmochimica Acta↗

An aem-tem study of weathering and diagenesis, Abert Lake, Oregon: I. Weathering reactions in the volcanics

Abert Lake in south-central Oregon provides a site suitable for the study of sequential weathering and diagenetic events. In this first of two papers, transmission electron microscopy was used to characterize the igneous mineralogy, subsolidus alteration assemblage, and the structural and chemical aspects of silicate weathering reactions that occur in the volcanic rocks (basalts, basaltic andesites, and dacitic/ rhyolitic extrusive and pyroclastics) that outcrop around the lake. Olivine and pyroxene replacement occurred topotactically, whereas feldspar and glass alteration produced randomly oriented smectite in channels and cavities. The tetrahedral, octahedral, and interlayer compositions of the weathering products, largely dioctahedral smectites, varied with primary mineral composition, rock type, and as the result of addition of elements released from adjacent reaction sites. Weathering of the highly evolved, Fe-rich Jug Mountain complex at the north end of the lake produced a homogeneous smectite assemblage that contrasts with the heterogeneous smectite assemblage replacing the volcanics along the eastern margin of the lake. The variability within and between the smectite assemblages highlights the microenvironmental diversity, fluctuating redox conditions, and variable solution chemistry associated with mineral weathering reactions in the surficial environment. Late-stage exhalative and aqueous alteration of the volcanics redistributed many components and formed a variety of alkali and alkali-earth carbonate, chloride, sulfate, and fluoride minerals in vugs and cracks. Overall, substantial Mg, Si, Na, Ca, and K are released by weathering reactions that include the almost complete destruction of the Mg-smectite that initially replaced olivine. The leaching of these elements from the volcanics provides an important source of these constituents in the lake water. The nature of subsequent diagenetic reactions resulting from the interaction between the materials transported to the lake and the solution will be described in part II ( Banfield et al., 1991).

Geochimica et Cosmochimica Acta↗

An AEM-TEM study of weathering and diagenesis, Abert Lake, Oregon: II. Diagenetic modification of the sedimentary assemblage

This paper compares the mineralogy and chemistry of clay minerals in sediments from various depths and positions in Abert Lake and surrounding playa with those of the weathered materials entering the lake in order to reveal the nature and extent of post-depositional mineralogical modification. Analytical electron microscope (AEM) data from individual clay particles reveal that each sample is comprised of a highly inhomogeneous smectite assemblage. The thin clay flakes (commonly less than 10 nm wide) display a complete range in octahedral sheet compositions from nearly dioctahedral to nearly trioctahedral. The very abundant Mg-rich lake smectites with an estimated composition K 0.29 (Al 0.23 -Mg 2.16 Fe 0.30 )Si 3.80 Al 0.20 O 10 (OH) 2 are not formed by weathering. This confirms the importance of diagenetic Mg uptake. Lattice-fringe imaging failed to reveal distinct brucite-like or vermiculite-like layers, suggesting that interstratifications of this type are rare or absent. Siliceous coatings on clay particles (identified by silica excess in smectite analyses) seem to favor topotactic overgrowth of stevensite rather than addition of brucite-like layers to the dioctahedral nuclei. The growth of K-stevensite dilutes the Al content of the crystal, and thus the increasing diagenetic modification reduces rather than supplements its illite component. Smectite compositions within individual samples were highly variable, yet source-related characteristics such as the abundance of Fe-rich smectite were apparent. Little evidence for systematic K or Mg enrichment with depth was identified in samples from depths of down to 16 feet below the sediment-water interface. The most magnesian assemblages are associated both with weathering sources of Mg-rich smectite and playa environments subjected to repeated wetting and drying cycles. Thus, the observations suggest that clay compositions primarily reflect changes in lake levels, brine composition, and source characteristics, rather than time and depth/compaction effects. Other diagenetic reactions in the sediment include recrystallization of Na-rich silica gel and diatom fragments. Abundant, submicron-sized, untwinned, euhedral crystals of K-feldspar are interpreted to be authigenic in origin.

Geochimica et Cosmochimica Acta↗

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. ?? 1990 Springer-Verlag.

Contributions to Mineralogy and Petrology↗