DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS     

Warren J. de Bruyn  Mike Harvey  Jill M. Cainey  Eric S. Saltzman 《Journal of Atmospheric Chemistry》2002,41(2):189-209

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.  相似文献   

Metal island growth and dynamics on molybdenite surfaces     

Udo Becker  Kevin M. Rosso  Michele Warren 《Geochimica et cosmochimica acta》2003,67(5):923-934

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.  相似文献   

FLUXES: A NEW PARADIGM FOR GEOLOGIC EDUCATION?     

Warren W. Wood 《Ground water》1997,35(1):1-1

  相似文献   

The Effects of Climate Change on Water Resources in the West: Introduction and Overview     

Tim Barnett  Robert Malone  William Pennell  Detlet Stammer  Bert Semtner  Warren Washington 《Climatic change》2004,62(1-3):1-11

The results of an experimental `end to end' assessment of the effects of climate change on water resources in the western United States are described. The assessment focuses on the potential effects of climate change over the first half of the 21st century on the Columbia, Sacramento/San Joaquin, and Colorado river basins. The paper describes the methodology used for the assessment, and it summarizes the principal findings of the study. The strengths and weaknesses of this study are discussed, and suggestions are made for improving future climate change assessments.  相似文献   

A preliminary investigation into the use of ochre as a remedial amendment in arsenic-contaminated soils     

M. Doi  G. Warren  M.E. Hodson   《Applied Geochemistry》2005,20(12):2207-2216

Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg⁻¹) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 μg kg⁻¹ in the control and 1–2.5 μg kg⁻¹ in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05–1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as solution concentration was reduced to ca. 1 μg kg⁻¹ by 0.2–1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 μg kg⁻¹ in the 1:1 ochre:soil mix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K = 1.64, n = 0.79, R² = 0.76, p 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area.  相似文献   

Using monazite and zircon petrochronology to constrain the P–T–t evolution of the middle crust in the Bhutan Himalaya          下载免费PDF全文

D. Regis  C. J. Warren  C. M. Mottram  N. M. W. Roberts 《Journal of Metamorphic Geology》2016,34(6):617-639

The growth and dissolution behaviour of accessory phases (and especially those of geochronological interest) in metamorphosed pelites depends on, among others, the bulk composition, the prograde metamorphic evolution and the cooling path. Monazite and zircon are arguably the most commonly used geochronometers for dating felsic metamorphic rocks, yet crystal growth mechanisms as a function of rock composition, pressure and temperature are still incompletely understood. Ages of different growth zones in zircon and monazite in a garnet‐bearing anatectic metapelite from the Greater Himalayan Sequence in NW Bhutan were investigated via a combination of thermodynamic modelling, microtextural data and interpretation of trace‐element chemical ‘fingerprint’ indicators in order to link them to the metamorphic stage at which they crystallized. Differences in the trace‐element composition (HREE, Y, Eu_N/Eu*_N) of different phases were used to track the growth/dissolution of major (e.g. plagioclase, garnet) and accessory phases (e.g. monazite, zircon, xenotime, allanite). Taken together, these data constrain multiple pressure–temperature–time (P–T–t) points from low temperature (<550 °C) to upper amphibolite facies (partial melting, >700 °C) conditions. The results suggest that the metapelite experienced a cryptic early metamorphic stage at c. 38 Ma at <550 °C, ≥0.85 GPa during which plagioclase was probably absent. This was followed by a prolonged high‐T, medium‐pressure (~600 °C, 0.55 GPa) evolution at 35–29 Ma during which the garnet grew, and subsequent partial melting at >690 °C and >18 Ma. Our data confirm that both geochronometers can crystallize independently at different times along the same P–T path and that neither monazite nor zircon necessarily provides timing constraints on ‘peak’ metamorphism. Therefore, collecting monazite and zircon ages as well as major and trace‐element data from major and accessory phases in the same sample is essential for reconstructing the most coherent metamorphic P–T–t evolution and thus for robustly constraining the rates and timescales of metamorphic cycles.  相似文献   

Development of a Highly Portable Plate Loading Device and In Situ Modulus Measurements in Weak Rock Masses     

Raj R. Kallu  Evan R. Keffeler  Robert J. Watters  Sean N. Warren 《Rock Mechanics and Rock Engineering》2016,49(2):443-454

  相似文献   

The historically adjusted range and the historically rescaled adjusted range     

E. H. Lloyd  D. Warren 《Stochastic Environmental Research and Risk Assessment (SERRA)》1988,2(3):175-188

It was remarked by Hurst in 1951 that the adjusted range gives the size of the smallest reservoir capable of providing a constant discharge equal to the mean inflow. Since that time this range and its rescaled modification, the Hurst range, have been widely discussed, not however primarily with a view to applying them to reservoir design problems, but rather on account of their possible relevance to the simulation of geophysical time series.Acknowledging the well-known conceptual weaknesses of adjusted ranges and the theoretical difficulties that inhibit their direct utilisation in the design and operation of real reservoirs, the authors argue that the interest displayed on ranges during the past few decades justifies the effort of eliminating one in particular of these weakness, namely their non-implementability as operating policies, a consequence of the fact that they can only be retrospectively evaluated. The paper proposes modifications in which the unknowable mean and standard deviation of future samples are replaced by the known mean and sample standard deviation of historical data, leading to the historically adjusted range and the historically rescaled and adjusted range. The latter is produced as an implementable approximation to Hurst's (1951) solution to the optimal reservoir problem.The expected values of the new ranges are evaluated and numerically tabulated.  相似文献   

Desertification as a Global environmental issue     

Andrew Warren 《GeoJournal》1993,31(1):11-14

Compared to other environmental issues, such as Global Warming/Climatic Change, and the Ozone Hole, Desertification has been neglected by both scientists and funding agencies. The reasons are the complexity of the problem and the poverty and marginality of the arid lands. The author suggests a policy-oriented definition and draws attention to the differences between drought, desiccation and dry-land degradation.  相似文献   

Suspended particulate grain size dynamics and their implications for trace metal sorption in the Don River     

Lesley A. Warren  Ann P. Zimmermann 《Aquatic Sciences - Research Across Boundaries》1994,56(4):348-362

We examined particle size distributions of suspended particulate matter (SPM); physical and environmental influences on the observed distributions; and relationships between particle size and geochemical partitioning of metals, over the fall and winter period in a small urban river (Don River, Toronto, Ontario, Canada). For this dataset, the majority of particles (80%) in suspension were less than 10 µm in size. In addition, while total SPM concentrations showed a positive trend with increasing discharge (Q); the proportions of particles found within given size classes were independent of both SPM concentration and Q. Temperature was the only measured environmental variable related to the particle concentrations within size classes. As water temperature increased, the concentration of particles in the smallest size class (1–4 µm) decreased, while the concentration of silt and/or algae sized particles (10–50 µm) increased. Increasing water temperatures may promote bacterial attachment to particles and their subsequent flocculation into larger sized particles. Decreasing concentrations of leachable (most labile) Cd, Zn and Mn were associated with increasing concentrations of the largest particles (70–150 µm) in suspension. In contrast, higher reducible (oxides) associated concentrations of Cd, Zn and Mn occurred with increasing concentrations of smaller particles (1–10 µm) in suspension. Both of these trends are speculated to reflect the importance of particle surface area for metal sorption reactions.  相似文献