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.     

Effect of pressure, temperature, and oxygen fugacity on the metal-silicate partitioning of Te, Se, and S: Implications for earth differentiation

We have measured liquid Fe metal-liquid silicate partitioning (D_i) of tellurium, selenium, and sulfur over a range of pressure, temperature, and oxygen fugacity (1-19 GPa, 2023-2693 K, fO₂ −0.4 to −5.5 log units relative to the iron-wüstite buffer) to better assess the role of metallic melts in fractionating these elements during mantle melting and early Earth evolution. We find that metal-silicate partitioning of all three elements decreases with falling FeO activity in the silicate melt, and that the addition of 5-10 wt% S in the metal phase results in a 3-fold enhancement of both D_Te and D_Se. In general, Te, Se, and S all become more siderophile with increasing pressure, and less siderophile with increasing temperature, in agreement with previous work. In all sulfur-bearing experiments, D_Te is greater than D_Se or D_S, with the latter two being similar over a range of P and T. Parameterized results are used to estimate metal-silicate partitioning at the base of a magma ocean which deepens as accretion progresses, with the equilibration temperature fixed at the peridotite liquidus. We show that during accretion, Te behaves like a highly siderophile element, with expected core/mantle partitioning of >10⁵, in contrast to the observed core/mantle ratio of ∼100. Less extreme differences are observed for Se and S, which yielded core/mantle partitioning 100- to 10 times higher, respectively, than the observed value. Addition of ∼0.5 wt% of a meteorite component (H, EH or EL ordinary chondrite) is sufficient to raise mantle abundances to their current level and erase the original interelement fractionation of metal-silicate equilibrium.     

Hydrocarbons generated by hydropyrolysis of suspended marine particulate organic matter: Relationship to the oceanography of the Black Sea and the Rhodes Gyre

The suspended particulate organic matter, SPOM, in the autumnal Black Sea has been characterised using catalytic hydropyrolysis (HyPy) of the total (bound plus free) lipid material. The technique, which generates maximum yields of volatile products from sediments, kerogens and phytoplankton, was followed using gas chromatography and gas chromatography/mass spectrometry. The generated alkanes were dominated by n-C₁₈, hypothesised to arise predominantly from unsaturated C₁₈ fatty acids. Steranes were generated from reductive conversion of free and bound sterols. The generation of branched alkanes and especially of hopanes provided formal evidence for the participation of bacteria in the mineralisation of the SPOM. Whereas similar distributions of n-alkanes were generated from SPOM sampled from different depths of the comparatively well-stirred Rhodes Gyre (eastern Mediterranean), mineralisation of the SPOM at each depth of the central Black Sea produced characteristic changes in the composition and concentration of the HyPy products. Depth profiles of the n-alkanes generated from SPOM in the region of the Rim Current were affected by the local hydrography. Polynuclear aromatic hydrocarbons (PAHs) of anthropogenic origin were present in the surface waters of the central Black Sea. Some methyl benzenes, thiophenes and pyrroles were also generated.     

Early and Middle Pleistocene landscapes of eastern England

This paper reviews the pattern of climate and environmental change in eastern England over the period of the Early and Middle Pleistocene, focussing especially upon northern East Anglia. Particular attention is given to the climate and tectonics that have brought about these changes and the distinctive geology, topography and biology that has developed. Throughout, an attempt is made to describe the new models that have been proposed for the Early and Middle Pleistocene of eastern England, and explain the reasons for these changes. The Early Pleistocene experienced relatively high insulation and relatively low magnitude climatic change and is represented primarily by non-climatically forced processes in the form of tidal current- and wave-activity which formed shallow marine deposits. It is possible to recognise a tectonic control in the distribution of deposits of this age because the surface processes do not have the power to remove this signature. The early Middle Pleistocene was dominated by higher magnitude climatic change involving, occasionally, climatic extremes that ranged from permafrost to mediterranean. The landscape at this time was dominated by the behaviour of major rivers (Thames, Bytham, Ancaster) and extensive coastal activity. In the latter part of the early Middle Pleistocene and the Late Middle Pleistocene the climate experienced major changes which resulted in periods of lowland glaciation and short intervals when the climate was warmer than the present. Details of tectonic activity are difficult to identify because they are removed by powerful surface processes, but it is possible to infer uplift focussed on the major interfluves of central England and subsidence in the North Seas basin. In the areas of glaciation the landscape changed radically from an organised terrain dominated by large rivers and extensive shallow coastal zones to complex, with small valleys, disrupted drainage and often discontinuous river, slope and coastal deposits. Likewise the switching off of the North Sea Delta and the opening of the Strait of Dover, separating Britain from continental Europe can be attributed to the onset of lowland glaciation. The case is made that eastern England was glaciated four times during the Middle Pleistocene: during MIS 16, 12, 10 and 6, and attention is given to recent evidence contradicting this model. Over the period of the Middle Pleistocene there is evidence for high biomass production occurring over short intervals coinciding with the climatic optima of MIS 19, 17, 15, 13, 11, and 7c, 7a and during most of these warmer periods, extending back to c. 750 ka (MIS 19/17), there is evidence in the region for the brief appearance of humans.     

The sediment infill of subglacial meltwater channels on the West Antarctic continental shelf

Subglacial meltwater plays a significant yet poorly understood role in the dynamics of the Antarctic ice sheets. Here we present new swath bathymetry from the western Amundsen Sea Embayment, West Antarctica, showing meltwater channels eroded into acoustic basement. Their morphological characteristics and size are consistent with incision by subglacial meltwater. To understand how and when these channels formed we have investigated the infill of three channels. Diamictons deposited beneath or proximal to an expanded grounded West Antarctic Ice Sheet are present in two of the channels and these are overlain by glaciomarine sediments deposited after deglaciation. The sediment core from the third channel recovered a turbidite sequence also deposited after the last deglaciation. The presence of deformation till at one core site and the absence of typical meltwater deposits (e.g., sorted sands and gravels) in all three cores suggest that channel incision pre-dates overriding by fast flowing grounded ice during the last glacial period. Given the overall scale of the channels and their incision into bedrock, it is likely that the channels formed over multiple glaciations, possibly since the Miocene, and have been reoccupied on several occasions. This also implies that the channels have survived numerous advances and retreats of grounded ice.     

Geochemistry and petrology of selected coal samples from Sumatra, Kalimantan, Sulawesi, and Papua, Indonesia

Indonesia has become the world's largest exporter of thermal coal and is a major supplier to the Asian coal market, particularly as the People's Republic of China is now (2007) and perhaps may remain a net importer of coal. Indonesia has had a long history of coal production, mainly in Sumatra and Kalimantan, but only in the last two decades have government and commercial forces resulted in a remarkable coal boom. A recent assessment of Indonesian coal-bed methane (CBM) potential has motivated active CBM exploration. Most of the coal is Paleogene and Neogene, low to moderate rank and has low ash yield and sulfur (generally < 10 and < 1 wt.%, respectively). Active tectonic and igneous activity has resulted in significant rank increase in some coal basins. Eight coal samples are described that represent the major export and/or resource potential of Sumatra, Kalimantan, Sulawesi, and Papua. Detailed geochemistry, including proximate and ultimate analysis, sulfur forms, and major, minor, and trace element determinations are presented. Organic petrology and vitrinite reflectance data reflect various precursor flora assemblages and rank variations, including sample composites from active igneous and tectonic areas. A comparison of Hazardous Air Pollutants (HAPs) elements abundance with world and US averages show that the Indonesian coals have low combustion pollution potential.     

Modifications of resonant column and torsional shear device for the large strain

Conventional RC/TS (resonant column and torsional shear) devices use a specimen with an aspect ratio (height-to-diameter) of 2:1 and this generates a maximum shear strain in the sample of about 1.5% at the maximum rotation of the driving system. The objective of this study is to modify the RC/TS device to generate higher strain amplitude. The modifications include a new base pedestal to overcome the limitations in the travel of the drive system and modification of the coil wiring to increase torque. The effects of the new coil wire on torque in the electromagnetic drive system were evaluated and the application of the modified device was illustrated using sand soil.