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

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%.     

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.     

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

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.     

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

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.     

Using monazite and zircon petrochronology to constrain the P–T–t evolution of the middle crust in the Bhutan Himalaya

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.     

Taxonomic Studies on a New Marine Ciliate, Apocoleps magnus gen. nov., spec. nov. （Ciliophora, Colepidae）, Isolated from Qingdao, China

The morphology and infraciliature of a new marine colepid ciliate, Apocoleps magnus gen. nov., spec. nov., are described based on living observations and silver impregnations. The new genus Apocoleps is characterized by having 8 (vs. 6 in most other related genera) armour tiers, spines at both ends of the cell, 3 adoral organelles and plates with 4 reniform uni-windows. Apocoleps magnus spec. nov. is defined by the following features: body elongated and slightly curved, about 100–120μm× 35–45 μm in vivo; an...     

Secondary‐volatiles linked metallic iron in eucrites: The dual‐origin metals of Camel Donga

The unique occurrence of abundant (~1 vol%) near‐pure‐Fe metal in the Camel Donga eucrite is more complicated than previously believed. In addition to that component of groundmass metal, scattered within the meteorite are discrete nodules of much higher kamacite abundance. We have studied the petrology and composition of two of these nodules in the form of samples we call CD2 and CD3. The nodules are ovoids 11 (CD2) to 15 (CD3) mm across, with metal, or inferred preweathering metal, abundances of 12–17 vol% (CD2 is unfortunately quite weathered). The CD3 nodule also includes at its center a 5 mm ovoid clumping (6 vol%) of F‐apatite. Both nodules are fine‐grained, so the high Fe metal and apatite contents are clearly not flukes of inadequate sampling. The metals within the nodules are distinctly Ni‐rich (0.3–0.6 wt%) compared to the pure‐Fe (Ni generally 0.01 wt%) groundmass metals. Bulk analyses of three pieces of the CD2 nodule show that trace siderophile elements Ir, Os, and Co are commensurately enriched; Au is enriched to a lesser degree. The siderophile evidence shows the nodules did not form by in situ reduction of pyroxene FeO. Moreover, the nodules do not show features such as silica‐phase enrichment or pyroxene with reduced FeO (as constrained by FeO/MgO and especially FeO/MnO) predicted by the in situ reduction model. The oxide minerals, even in groundmass samples well away from the nodules, also show little evidence of reduction. Although the nodule boundaries are generally sharp, groundmass‐metal Ni content is anti‐correlated with distance from the CD3 nodule. We infer that the nodules represent materials that originated within impactors into the Camel Donga portion of the eucrite crust, but probably were profoundly altered during later metamorphism/metasomatism. Origin of the pure‐Fe groundmass metal remains enigmatic. In situ reduction probably played an important role, and association in the same meteorite of the Fe‐nodules is probably significant. But the fluid during alteration was probably not (as previously modeled) purely S and O, of simple heat‐driven internal derivation. We conjecture a two‐stage metasomatism, as fluids passed through Camel Donga after impact heating of volatile‐rich chondritic masses (survivors of gentle accretionary impacts) within the nearby crust. First, reduction to form troilite may have been triggered by fluids rich in S₂ and CO (derived from the protonodules?), and then in a distinct later stage, fluids were (comparatively) H₂O‐rich, and thus reacted with troilite to form pure‐Fe metal along with H₂S and SO₂. The early eucrite crust was in places a dynamic fluid‐bearing environment that hosted complex chemical processes, including some that engendered significant diversity among metal+sulfide alterations.     

The historically adjusted range and the historically rescaled adjusted range

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.