Biogenic nanoparticulate UO2: Synthesis, characterization, and factors affecting surface reactivity

The surface reactivity of biogenic, nanoparticulate UO₂ with respect to sorption of aqueous Zn(II) and particle annealing is different from that of bulk uraninite because of the presence of surface-associated organic matter on the biogenic UO₂. Synthesis of biogenic UO₂ was accomplished by reduction of aqueous uranyl ions, by Shewanella putrefaciens CN32, and the resulting nanoparticles were washed using one of two protocols: (1) to remove surface-associated organic matter and soluble uranyl species (NAUO2), or (2) to remove only soluble uranyl species (BIUO2). A suite of bulk and surface characterization techniques was used to examine bulk and biogenic, nanoparticulate UO₂ as a function of particle size and surface-associated organic matter. The N₂-BET surface areas of the two biogenic UO₂ samples following the washing procedures are 128.63 m² g⁻¹ (NAUO2) and 92.56 m² g⁻¹ (BIUO2), and the average particle sizes range from 5-10 nm based on TEM imaging. Electrophoretic mobility measurements indicate that the surface charge behavior of biogenic, nanoparticulate UO₂ (both NAUO2 and BIUO2) over the pH range 3-9 is the same as that of bulk. The U L_III-edge EXAFS spectra for biogenic UO₂ (both NAUO2 and BIUO2) were best fit with half the number of second-shell uranium neighbors compared to bulk uraninite, and no oxygen neighbors were detected beyond the first shell around U(IV) in the biogenic UO₂. At pH 7, sorption of Zn(II) onto both bulk uraninite and biogenic, nanoparticulate UO₂ is independent of electrolyte concentration, suggesting that Zn(II) sorption complexes are dominantly inner-sphere. The maximum surface area-normalized Zn(II) sorption loadings for the three substrates were 3.00 ± 0.20 μmol m⁻² UO₂ (bulk uraninite), 2.34 ± 0.12 μmol m⁻² UO₂ (NAUO2), and 2.57 ± 0.10 μmol m⁻² UO₂ (BIUO2). Fits of Zn K-edge EXAFS spectra for biogenic, nanoparticulate UO₂ indicate that Zn(II) sorption is dependent on the washing protocol. Zn-U pair correlations were observed at 2.8 ± 0.1 Å for NAUO2 and bulk uraninite; however, they were not observed for sample BIUO2. The derived Zn-U distance, coupled with an average Zn-O distance of 2.09 ± 0.02 Å, indicates that Zn(O,OH)₆ sorbs as bidentate, edge-sharing complexes to UO₈ polyhedra at the surface of NAUO2 nanoparticles and bulk uraninite, which is consistent with a Pauling bond-valence analysis. The absence of Zn-U pair correlations in sample BIUO2 suggests that Zn(II) binds preferentially to the organic matter coating rather than the UO₂ surface. Surface-associated organic matter on the biogenic UO₂ particles also inhibited particle annealing at 90 °C under anaerobic conditions. These results suggest that surface-associated organic matter decreases the reactivity of biogenic, nanoparticulate UO₂ surfaces relative to aqueous Zn(II) and possibly other environmental contaminants.     

Asymmetric vegetation responses to mid-Holocene aridity at the prairie-forest ecotone in south-central Minnesota

The mid-Holocene (ca. 8000-4000 cal yr BP) was a time of marked aridity throughout much of Minnesota, and the changes due to mid-Holocene aridity are seen as an analog for future responses to global warming. In this study, we compare the transition into (ca. 9000-7000 yr ago) and out of (ca. 5000-2500 yr ago) the mid-Holocene (MH) period at Kimble Pond and Sharkey Lake, located along the prairie forest ecotone in south-central Minnesota, using high resolution (∼ 5-36 yr) sampling of pollen, charcoal, sediment magnetic and loss-on-ignition properties. Changes in vegetation were asymmetrical with increasing aridity being marked by a pronounced shift from woodland/forest-dominated landscape to a more open mix of grassland and woodland/savanna. In contrast, at the end of the MH, grassland remained an important component of the landscape despite increasing effective moisture, and high charcoal influxes (median 2.7-4.0 vs. 0.6-1.7 mm² cm^− 2 yr^− 1 at start of MH) suggest the role of fire in limiting woodland expansion. Asymmetric vegetation responses, variation among and within proxies, and the near-absence of fire today suggest caution in using changes associated with mid-Holocene aridity at the prairie forest boundary as an analog for future responses to global warming.     

High-frequency sequences and their stacking patterns: sequence-stratigraphic evidence of high-frequency eustatic cycles

A hierarchy of interpreted eustatic cyclicity in siliciclastic sedimentary rocks has a pattern of superposed cycles with frequencies in the ranges of 9–10 m.y., 1–2 m.y., 0.1–0.2 m.y., and 0.01–0.02 m.y. (second- through fifth-order cyclicity, respectively). Stratigraphic units displaying this cyclicity include composite sequences, sequences, and parasequences. On the Exxon global cycle chart, fundamental third-order cycles (1–2 m.y. average duration) stack into related groups (second-order cycles: 9–10 m.y. duration). A much larger pattern (about 200 m.y.) is interpreted as tectonically controlled eustasy probably related to sea-floor spreading rates.

One and probably two higher orders of cyclicity (fourth-order: 0.1–0.2 m.y.; and fifth-order: 0.01–0.02 m.y.) are now observed in work with well logs, cores, and outcrops in areas of very rapid deposition. These frequencies are in the range of Milankovitch cycles, and may represent part of the Milankovitch hierarchy which has been widely interpreted for cyclical units in carbonate rocks.

High-frequency (fourth-order) sequences, which form at a 0.1–0.2 m.y. cyclicity, have all the stratal attributes of conventional sequences, including constituent parasequences and systems tracts, and play a dominant role controling reservoir, source, and sealing rock distribution. A consistent hierarchy of stratigraphy is observed. Parasequences (probable fifth-order cyclicity) stack into sets to form systems tracts in fourth-order sequences. Groups (sets) of fourth-order sequences are deposited between major third-order boundaries within third-order composite sequences. Sequences in these sets stack in prograding and backstepping patterns to form third-order lowstand, transgressive, and highstand sequence sets.

Third-order sequence boundaries are marked by greater basinward shifts in facies, by larger more widespread incised valleys, and by more extensive onlap than are fourth-order sequence boundaries. Third-order condensed sections commonly are widespread, faunally rich, and widely correlated biozone and mapping markers. Fourth-order sequence analysis helps to understand reservoir, source, and seal distribution at the play and prospect scale. An example from the Gulf of Mexico is discussed.     

A modeling of the structure and compressibility of quartz with a molecular potential and its transferability to cristobalite and coesite

Several computer models of quartz were developed and tested. A simple model based on a potential energy function, derived in large part from quantum mechanical calculations on the molecule H₆Si₂O₇, was found to reproduce the compressibility curve for quartz up to pressures of 8 GPa. The potential includes quadratic expressions for the SiO bond lengths, the OSiO angles and a parameter spanning the SiOSi angle together with an exponential OO repulsion term for non co-dimer O atoms. The variations in the cell edges and in the SiOSi angle, as a function of pressure, parallel observed trends when the bond lengths and angles calculated for the molecule are used as rgressor values. Poisson ratios calculated using the model match those observed. Two configurations for quartz related by the Dauphiné twin law are generated as minimum energy structures of the model with about equal frequencies as observed in nature. It is shown that the model, devised for quartz, can also be applied to the silica polymorph cristobalite, giving reasonable estimates of its compressibility curve, structural parameters and its negative Poisson ratio. When the observed bond lengths and angles are used as regressor values, the model generates the absolute coordinates of the atoms and the cell dimensions for quartz to within 0.005 Å and those of cristobalite to within 0.001 Å, on average, both at zero pressure. When applied to coesite, the model yields a zero pressure structure that is close to that observed but which is significantly softer than observed. The resulting SiO bond lengths are linearly correlated with f _s (O), as observed for coesite, despite the use of a single bond length and a single SiOSi angle as regressor values in the calculation. When the structures are optimized assuming P1 space group symmetry and triclinic cell dimensions, the resulting frameworks of silicate tetrahedra exhibit the translational, rotational and reflection symmetries observed for quartz, cristobalite and coesite. The fact that the resulting frameworks exhibit observed space group symmetries is evidence that the symmetry adopted by the silica polymorphs can be explained by short ranged forces.     

Interaction of glucose and cellulose with hydrogen sulphide and polysulphides

This paper describes simulation experiments in which glucose and cellulose were reacted with polysulphide and hydrogen sulphide at ambient temperatures in an aqueous environment. Organic sulphur containing compounds were formed that yield several thiophenes upon pyrolysis/evaporation. The experiments show that interaction of carbohydrates with hydrogen sulphide or polysulphides is a possible way for carbohydrates to react in very recent sediments. From the results of this study it can be concluded that carbohydrate carbon can be preserved in sediments in a form that is resistant to microbial attack and that will have a greater potential for survival during diagenesis than the carbohydrate precursor.     

Estimating the crush zone size under a cutting tool in coal

Summary As part of an effort to understand the mechanics of fine fragment formation in coal, which is important in studies of respirable dust due to mining, fracture toughness measurements and the strain energy density (SED) theory were applied to calculate the crush zone size under a cutting tool in coal. This zone is the major source of fine fragments in the 1 to 10 µm size range. The model used in these calculations is a boundary element program containing a failure criterion based on the SED theory. The boundary element program calculates linear elastic stresses at numerous points in the coal material ahead of a cutting bit. These stresses are then input to a subroutine called critical flaw length and orientation (CFLO) which uses the SED theory to determine the CFLO for a small crack at the boundary element stress computation point. The extent of crushing is based on earlier postulates about the role of inherent flaws in a fragmentation process. To form 1 to 10 µm fragments requires firstly a local stress strong enough to activate flaws with a characteristic length less than 1 to 10 µm and secondly, a flaw density sufficient to provide an average spacing between flaws also on the order of 1 to 10 µm. The locus of active 10 µm flaws represents the maximum possible extent of fine fragmentation in the 10 µm or less size range assuming that a sufficient inherent flaw density exists. The approach offers a first order approximation to the extent of crushing under a tool tip. The size and shape of the crush zone volume is affected by the attack angle and geometry of the tool.     

Threshold of motion of bivalve and gastropod shells under oscillatory flow in flume experiments

The threshold of motion of non-fragmented mollusc shells was studied for the first time under oscillatory flow. In this regard, flume experiments were used to investigate the threshold of motion of three bivalve and three gastropod species, two typical mollusc classes of coastal coquina deposits. The sieve diameters ranged from 2·0 to 15·9 mm. These experiments were performed on a flat-bottom setup under regular non-breaking waves (swell) produced by a flap-type wave generator. The critical Shields values for each species of mollusc were plotted against the sieve and nominal diameter. Moreover, the dimensionless Corey shape factor of the shells was evaluated in order to investigate the effect of mollusc shell shapes on the threshold of motion. According to their critical Shields parameter, the mollusc threshold data under oscillatory flow present smaller values than the siliciclastic sediments when considering their sieve diameter. In addition, the mollusc datasets are below the empirical curves built from siliciclastic grain data under current and waves. When considering the nominal diameter, the critical Shields parameter increases and the mollusc data are closer to siliciclastic sediments. Bivalves, which have a flat-concave shape (form factor: 0·27 to 0·37), have a higher critical Shields parameter for smaller particles and more uniform datasets than the gastropod scattered data, which have a rounded shape (form factor: 0·58 to 0·62) and have varied morphologies (ellipsoidal, conical and cubic). The comparison between previous current-driven threshold data of bioclastic sediment motion and the data of mollusc whole shells under oscillatory flow shows a fair correlation on the Shields diagram, in which all datasets are below the mean empirical curves for siliciclastic sediments. These findings indicate that the shape effect on the transport initiation is predominant for smaller shells. The use of the nominal diameter is satisfactory to improve the bioclastic and siliciclastic data correlation.     

Hydrogeological characterization of Gold Valley: an investigation of precipitation recharge in an intermountain basin in the Death Valley region, California, USA

Gold Valley is typical of intermountain basins in Death Valley National Park (DVNP), California (USA). Using water-balance calculations, a GIS-based analytical model has been developed to estimate precipitational infiltration rates from catchment-scale topographic data (elevation and slope). The calculations indicate that groundwater recharge mainly takes place at high elevations (>1,100?m) during winter (average 1.78?mm/yr). A resistivity survey suggests that groundwater accumulates in upstream compartmentalized reservoirs and that the groundwater flows through basin fill and fractured bedrock. This explains the relationship between the upstream precipitational infiltration in Gold Valley and the downstream spring flow in Willow Creek. To verify the ability of local recharge to support high-flux springs in DVNP, a GIS-based model was also applied to the Furnace Creek catchment. The results produced insufficient total volume of precipitational infiltration to support flow from the main high-flux springs in DVNP under current climatic conditions. This study introduces a GIS-based infiltration model that can be integrated into the Death Valley regional groundwater flow model to estimate precipitational infiltration recharge. In addition, the GIS-based model can efficiently estimate local precipitational infiltration in similar intermountain basins in arid regions provided that the validity of the model is verified.     

Structural controls on fractured coal reservoirs in the southern Appalachian Black Warrior foreland basin

Coal is a nearly impermeable rock type for which the production of fluids requires the presence of open fractures. Basin-wide controls on the fractured coal reservoirs of the Black Warrior foreland basin are demonstrated by the variability of maximum production rates from coalbed methane wells. Reservoir behavior depends on distance from the thrust front. Far from the thrust front, normal faults are barriers to fluid migration and compartmentalize the reservoirs. Close to the thrust front, rates are enhanced along some normal faults, and a new trend is developed. The two trends have the geometry of conjugate strike-slip faults with the same σ₁ direction as the Appalachian fold-thrust belt and are inferred to be the result of late pure-shear deformation of the foreland. Face cleat causes significant permeability anisotropy in some shallow coal seams but does not produce a map-scale production trend.     

Ophiolite complexes as collision zone markers: making the case for the Antique Ophiolite Complex, Panay Island, central Philippines

The collision between the North Palawan Block (NPB) and Philippine Mobile Belt (PMB) has been the subject of studies considering its significance in help-ing define the tectonic evolution of the Philippine is-land arc system. The geology of the western Panay island reveals the presence of a continent-related block (Buruanga Peninsula) juxtaposed to an oceanic frag-ment (Antique Ophiolite Complex). Our recent work in the Buruanga Peninsula helped us define the terrane boundary between the Peninsula and the Antique Ophiolite Complex. However, considering available published data, the Antique Ophiolite Complex has never been considered to be a part of the NPB and to mark the collision zone between Palawan and the PMB.