Metal island growth and dynamics on molybdenite surfaces

In order to understand the adsorption mechanism of metal atoms to semiconducting surfaces, we have studied, as a model system, the vapor phase adsorption of Ag, Au, and Cu on the (001) surface of molybdenite (MoS₂) and the subsequent surface diffusion of these adsorbates. Our scanning tunneling microscopy (STM) images show that, depending on the type of metal atom that is adsorbed, islands of a characteristic size (2 nm for Ag, 8 to 10 nm for Cu, two distinct sizes of 2 nm and 8 to 10 nm for Au), shape (well rounded in the lateral extension) and thickness (one monolayer for Ag, 1 to 1.5 nm for Cu) are formed during the initial stages of deposition. Whole islands are observed to surface diffuse without loss of size or shape. Despite the relatively large size of the copper islands on molybdenite, these islands surface diffuse extensively, suggesting that the Cu-S interaction is weak. Surface diffusion is only hindered once individual islands start to coalesce. As copper islands accumulate, the size and shape of the original islands can still be recognized, supporting the conclusion that these characteristics are constant and that monolayer growth occurs by the aggregation of islands across the surface.The strength and the nature of the Ag-S(MoS₂) bond were further investigated by using molecular orbital calculations, ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS). By applying quantum mechanical approaches using a two-dimensional periodic molybdenite slab and hexagonal MoS₂ clusters of different sizes with metal atoms adsorbed to them, it is possible to calculate the electron transfer between the mineral surface and the metal atom as well as the adsorption energy as a function of surface coverage. In addition, we used the results from the quantum mechanical runs to derive empirical potentials that model the characteristics of the forces within the crystal, within the adsorbed islands, and the metal and mineral surface. The combination of quantum mechanical calculations and empirical force field calculations explain the electronic structure and the highest stability of Ag islands that have seven atoms in diameter, which exactly agrees with the size of experimentally observed islands. UPS results also suggest that a specific new state is formed (approximately 4.5 eV into the valence band) which may describe the Ag-S bond because it does not occur in pure silver or molybdenite.This study shows how the combination of microscopic (STM), spectroscopic (STS, UPS), compositional (X-ray photoelectron spectroscopy, XPS) and molecular modeling (quantum mechanical and empirical) techniques is a useful approach to understand the nature of the metal to sulfide bond. Further insights may be gained concerning the natural association of certain metals with sulfides.     

Radiocarbon chronology of Holocene hydrologic changes in northeastern Mali

A detailed chronology of hydrological changes that occurred in northeastern Mali during the Holocene is based on approximately 30 ¹⁴C dates of molluscs which were collected from the lacustrine and paludal deposits of the Ine Sakane sand sea. The presence of cemented paleodunes indicates that the end of the Pleistocene was and arid period. This was followed by an early Holocene lacustrine episode (ca. 9500–6500 yr B.P.) during which numerous lakes occupied depressions formed in the Cretaceous limestones and between the sand ridges. These lakes reflect a significant rise in the water table. Between ca. 6500 and 5500 yr B.P. the lakes dried up, although the water table remained close to the ground surface in several areas. Calcareous concretions formed at the water table fringe during this time, thereby “fossilizing” some of the middle Holocene dunes. A second lacustrine episode is dated between ca. 5500 and 4500 yr B.P.; it corresponds to the establishment of numerous Neolithic settlements in the area. Arid conditions have developed since about 4500 yr B.P. to attain the conditions of the present day. The isotopic composition (¹⁸O and ¹³C) of the fauna reflects highly variable hydrological conditions. Groundwaters were recharged by precipitation which was occasionally very depleted in heavy oxygen (δ¹⁸O ? ?13%.). Evaporation induced an enrichment in ¹⁸O; high concentrations characterize some lakes. The ¹³C content of fossil shells reflect: (1) species ecological requirements, (2) isotopic composition of the total inorganic dissolved carbon (TIDC) in groundwaters, and (3) the lake metabolism.     

Electron tunneling properties of outer-membrane decaheme cytochromes from Shewanella oneidensis

We have characterized the outer-membrane decaheme cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 at the single-molecule level using scanning tunneling microscopy (STM) and tunneling spectroscopy (TS). These cytochrome proteins are of great interest because they are thought to mediate bacterial electron transfer reactions in anoxic waters that control the reductive dissolution of oxide minerals. In our study, to characterize the electron transfer properties of these proteins on a model surface, the purified cytochromes were chemically immobilized as molecular monolayers on Au(111) substrates via a recombinant tetra-cysteine sequence as verified by X-ray photoelectron spectroscopy. Atomic force microscopy images confirm the monolayer films were ∼5-8 nm thick which is consistent with the apparent lateral dimensions of individual cytochrome molecules obtained with STM. Current-voltage TS of single cytochrome molecules revealed that OmcA and MtrC have different abilities to mediate tunneling current despite having otherwise very similar molecular and biochemical properties. These observations suggest that, based on their electron tunneling properties, the two cytochromes could have specific roles during bacterial metal reduction. Additionally, this study establishes single-molecule STM/TS as an effective means for revealing insights into biogeochemical redox processes in the environment.     

Direct evidence of Middle Oligocene extension in the Calabria–Peloritani terrane from co-seismic faulting: the pseudotachylyte-bearing shear zones of Palmi (southern Calabria, Italy)

The Variscan crystalline basement of the Calabria–Peloritani terrane (CPT) in southern Italy was partly reworked by ductile and brittle shear zones throughout the Alpine tectonic evolution (from thickening to exhumation). Although evidence of extensional tectonics in the CPT has already been found and roughly constrained to the Oligocene onward, no attempt has ever been made to directly date brittle fault movements. Structural (meso- and micro-scale), kinematic and petrographic analyses and ⁴⁰Ar–³⁹Ar laser experiments reveal that the pseudotachylyte-bearing shear zones of the Palmi area in southern Calabria formed in response to extensional shearing ∼33.5 Ma ago and overprinted compressional tectonic structures. Results provide the first direct evidence of Middle Oligocene co-seismic faulting in the area and confirm the role of extensional tectonics in promoting the Oligocene exhumation of the Calabria basement.     

Vorticity analysis of the Palmi shear zone mylonites: new insights for the Alpine tectonic evolution of the Calabria–Peloritani terrane (southern Italy)

New microstructural data on the mylonites from the well‐exposed Palmi shear zone (southern Calabria) are presented with the aim to shed light on both the kinematics and the geometry of the southwestern branch of the Alpine belt during Eocene. In the study area, located between the Sardinia–Corsica block and the Calabria–Peloritani terrane, previous large‐scale geodynamic reconstructions suggest the presence of strike–slip or transform fault zones dissecting the southwestern branch of the Alpine belt. However, there are no field data supporting the occurrence of these structures. This paper uses vorticity analysis technique based on the aspect ratio and the long axis orientation of rigid porphyroclasts in mylonitic marbles and mylonitic granitoids, to estimate the contribution of pure and simple shear of deformation during the movement of the Palmi shear zone. Porphyroclasts aspect ratio and orientation were measured on thin sections using image analysis. Estimates of the vorticity number, W_m, indicate that the Palmi shear zone recorded general shear with a contribution of pure shear of c. 65%. Then, the Palmi shear zone can be interpreted as a segment of a left‐lateral transpressive bend along the southern termination of the Eocene Alpine front. Copyright © 2015 John Wiley & Sons, Ltd.     

Sulphate reduction in the sediment of the Venice canals (Italy)

The sulphur cycle in the sediment of the Venice canal network was investigated by considering the sulphate reduction rate (SRR) and the distribution of sulphur compounds, in both pore water and sediment. Sulphate reduction (SR) is the main process in the metabolism of the organic matter supplied to the network by untreated urban effluents. Although it might account for the decomposition of only a limited percentage of the total organic-C inputs, the estimated rates are among the highest observed in coastal sediments. Measured rates range from 0.26 to 0.99 micromolcm(-3)d(-1), while mean annual values, estimated by a diagenetic model, vary from 0.16 to 0.43 micromolcm(-3)d(-1). The speciation of S in the sediment reveals that pyrite-S is the most abundant component of the total reduced S pool, whereas acid volatile sulphides and elemental sulphur together account for less than 45%. A preliminary budget indicates that the rate of burial of solid-phase S is small compared to the S produced by SR (from 10 to 25%). A large amount of reduced S is then lost from the canal deposits to be re-oxidised at the sediment-water interface or in the overlying water column.     

Pauling bond strength, bond length and electron density distribution

The power law regression equation, <R(M–O)> = 1.46(<ρ(r _c)>/r)^?0.19, relating the average experimental bond lengths, <R(M–O)>, to the average accumulation of the electron density at the bond critical point, <ρ(r _c)>, between bonded pairs of metal and oxygen atoms (r is the row number of the M atom), determined at ambient conditions for oxide crystals, is similar to the regression equation R(M–O) = 1.41(ρ(r _c)/r)^?0.21 determined for three perovskite crystals at pressures as high as 80 GPa. The pair are also comparable with the equation <R(M–O)> = 1.43(<s>/r)^?0.21 determined for oxide crystals at ambient conditions and <R(M–O)> = 1.39(<s>/r)^?0.22 determined for geometry-optimized hydroxyacid molecules that relate the geometry-optimized bond lengths to the average Pauling bond strength, <s>, for the M–O bonded interactions. On the basis of the correspondence between the equations relating <ρ(r _c)> and <s> with bond length, it seems plausible that the Pauling bond strength might serve a rough estimate of the accumulation of the electron density between M–O bonded pairs of atoms. Similar expressions, relating bond length and bond strength hold for fluoride, nitride and sulfide molecules and crystals. The similarity of the expressions for the crystals and molecules is compelling evidence that molecular and crystalline M–O bonded interactions are intrinsically related. The value of <ρ(r _c)> = r[(1.41)/<R(M–O)>]^4.76 determined for the average bond length for a given coordination polyhedron closely matches the Pauling’s electrostatic bond strength reaching each the coordinating anions of the coordinated polyhedron. Despite the relative simplicity of the expression, it appears to be more general in its application in that it holds for the bulk of the M–O bonded pairs of atoms of the periodic table.     

SiO bonded interactions in coesite: a comparison of crystalline, molecular and experimental electron density distributions

Bond critical point properties of electron density distributions calculated for representative Si₅O₁₆ moieties of the structure of coesite are compared with those observed and calculated for the bulk crystal. The values calculated for the moieties agree with those observed to within ∼5%, on average, whereas those calculated for the crystal agree to within ∼10%. As the SiOSi angles increase and the SiO bonds shorten, there is a progressive build-up in the calculated electron density along the bonds. This is accompanied by an increase in both the curvatures of the electron density, both perpendicular and parallel to each bond, and the Laplacian of the electron density distribution at the bond critical points. The cross sections of the bonds at the critical points become more circular as the angle approaches 180o. Also, the bonded radius of the oxide anion decreases about twice as much as that of the Si cation as the SiO bond length decreases and the fraction of s-character of the bond is indicated to increase. A knowledge of electron density distributions is central to our understanding of the forces that govern the structure, properties, solid state reactions, surface reactions and phase transformations of minerals. The software (CRYSTAL95 and TOPOND) used in this study to calculate the bond critical properties of the electron density and Laplacian distributions is bound to promote a deeper understanding of crystal chemistry and properties. Received: 23 February 1998 / Revised, accepted: 16 July 1998     

Ecosystem under pressure: ballast water discharge into Galveston Bay, Texas (USA) from 2005 to 2010

Ballast water exchange processes facilitate the dispersal and unnatural geographic expansion of phytoplankton, including harmful algal bloom species. From 2005 to 2010, over 45,000 vessels (≈ 8000 annually) travelled across Galveston Bay (Texas, USA) to the deep-water ports of Houston (10th largest in the world), Texas City and Galveston. These vessels (primarily tankers and bulkers) discharged ≈ 1.2 × 10(8) metrictons of ballast water; equivalent to ≈ 3.4% of the total volume of the Bay. Over half of the ballast water discharged had a coastwise origin, 96% being from US waters. Galveston Bay has fewer non-indigenous species but receives a higher volume of ballast water discharge, relative to the highly invaded Chesapeake and San Francisco Bays. Given the magnitude of shipping traffic, the role of Galveston Bay, both as a recipient and donor region of non-indigenous phytoplankton species is discussed here in terms of the invasibility risk to this system by way of ballast water.     

Flow prediction in high altitude ungauged catchments: A case study in the Italian Alps (Pantano Basin,Adamello Group)

We develop a simple model to evaluate the daily flow discharges in the ablation season for the 11 km² Pantano basin in the Retiche Italian Alps, based upon the data gathered during a three years field campaign. The Pantano basin embeds the Venerocolo debris covered and the Avio debris free glaciers, covering 2.14 km² in the Adamello Group, where the widest Italian glacier Adamello is located. First, degree-day models based upon air temperature are tuned to calculate snow and ice melt at daily scale. Glaciers’ meteorological data are collected from an automatic weather station (AWS), operating on the glacier during summer 2007. The melt factors in the debris covered areas of the glacier are estimated against debris thickness, using a data driven parameterization. The flow discharge from the catchment is estimated using semi distributed flow routing for the ablation seasons of four years, from 2006 to 2009. The predicted discharges are compared to those derived from inverse reservoir's routing at the Benedetto lake, catching the basin outflow. The proposed approach is valuable as a tool to investigate the hydrology of poorly gauged glacierized areas, including those with debris covered ice, widely diffused and yet poorly understood. Pending accurate parameterization the approach is usable for water resources evaluation and for long term assessment of the climate change impact on the glacierized areas within the Alps.