Structural controls and mechanisms of diffusion in natural silicate melts

The diffusion properties of Na, Cs, Ba, Fe and Eu ions have been determined experimentally for a pantellerite melt and of these ions plus Li, Mn and Co in pitchstone melt, using the radiotracer residual-activity method, and narrow platinum capillaries, over the temperature range 1,200–1,400° C. In addition, Eu diffusion in a basaltic and an andesitic melt was determined. Diffusion of all cations follows an Arrhenius relationship, activation energy values being high for diffusion in the pantellerite melt (e.g. Eu: 100 kcal mol^–1) except in the case of Na (24.3 kcal mol^–1). Activation energies of diffusion in the pitchstone melt are similar to values recorded earlier for andesitic and basaltic melts.The new data are used, along with previously published data for diffusion in other composition melts, to examine the compositional and structural controls on diffusion. The range of diffusivities shows a marked change with melt composition; over two orders of magnitude for a basaltic melt, and nearly four orders for a pantellerite melt (both at 1,300° C). Diffusivity of all cations (except Li and Na) correlates positively with the proportion of network modifying cations. In the case of Li and Na the correlation is negative but the diffusivity of these ions correlates positively with the proportion of Na or of Na + K ions in the bulk melt. Diffusion behaviour in the pantellerite melt departs from the relationships shown by the data for other melt compositions, which could be partly explained by trivalent ions (such as Fe) occupying network forming positions. The diffusivity of alkali metal ions is strongly dependent on ionic radius, but this is not the case with the divalent and trivalent ions; diffusivity of these ions remains relatively constant with change in radius but decreases with increase in ionic charge.A compensation diagram shows four distinct but parallel trends for the majority of the cations in four melt types but the data for Li and Na plot on a separate trend. This and the other relationships are used to elucidate possible mechanisms of diffusion. Exchange mechanisms appear to be common, with the preservation of local charge balance. Li and Na diffuse by a distinct mechanism which involves exchange of similar or identical ions. The diffusion behaviour of the smaller alkali metal ions is sufficiently distinct from all other cations to indicate that diffusion could be an important factor in the geochemical fractionation of the alkali elements.s     

The behaviour of tungsten in granitic melt-vapour systems

An experimental study has been carried out to determine the effect of solution composition on the partitioning behaviour of tungsten in granitic melt-vapour systems at 800° C and 1 kbar. With chloride and phosphate solutions, tungsten partitions strongly into the aqueous phase, whereas with fluoride, carbonate and borate solutions, and water alone, tungsten partitions in favour of the melt. With chloride solutions, the fluid/melt partition coefficients (K _D) for W show a marked positive correlation with chloride concentration, and suggest that at low chloride concentrations W-Cl complexes with low Cl∶W ratios (such as associated equivalents of (WO₃)₂C1⁻) may be present. In contrast, at higher chloride concentrations complexes with high Cl∶W ratios (such as WOCl₄, WCl₆ and associated ionic equivalents) may predominate. With phosphate solutions, K _D shows little variation with phosphate concentration, and phosphorus heteropolytungstates (such as H₃[PW₁₂O₄₀]) may be present. There is no evidence to suggest that fluoride, carbonate or borate complexes of tungsten are important under the experimental conditions: the data for these compositions can be interpreted assuming that isopolytungstates (such as H₆[H₂W₁₂O₄₀]) are present. Within high temperature hydrothermal solutions tungsten may be transported principally as isopolytungstates and heteropolytungstates in addition to chloride complexes, and this may, in part, account for the common association of apatite and arsenopyrite with scheelite and wolframite in tungsten deposits.     

Temperature-dependent Fe2+–Mn2+ order–disorder behaviour in amphiboles

The partitioning of Fe and Mn between the large M(4) site and the octahedral sites, M(1,2,3) in the amphibole structure has been investigated in two natural manganogrunerites of compositions Ca_0.1Mn_1.9 Mg_1.25Fe²⁺ _3.56Fe³⁺ _0.38Si_7.81O₂₂(OH)₂ and Ca_0.24Mn_1.57 Mg_2.27 Fe²⁺ _2.76Fe³⁺ _0.32Si_7.84O₂₂(OH)₂. The long-range cation distribution in the two samples has been elucidated by in situ neutron powder diffraction revealing that Mn is preferentially ordered onto M(4) ? M(2) >M(1) >M(3) in both samples. Partitioning of Mn from M(4) into the octahedral sites begins at 350 °C, with site exchange energies of ?16.6 kJ mol^?1 and ?14.9 kJ mol^?1, in samples containing 1.90 and 1.57 Mn apfu, respectively. Mössbauer and infrared spectroscopy have been used to study the samples at room temperature, and Mössbauer data agree well with the diffraction results, confirming that high-temperature cation distributions are retained during cooling. The fine structure in the hydroxyl-stretching region of the IR absorption spectra has been used to discuss qualitatively the site occupancies of the coordinating M(1)M(3)M(1) triplet, linked by O(3). On the basis of such modelling, we conclude that a degree of local clustering is present in both samples.     

The age and growth of hottentot seabream Pachymetopon blochii before and after the South African linefish state of emergency in 2000

The hottentot seabream Pachymetopon blochii is a small-sized (maximum 2.67 kg) sparid endemic to southern Africa. It is an important target in South Africa's Western Cape traditional linefishery, particularly in the absence of more valuable pelagic species (such as Thyrsites atun and Seriola lalandi). In 2000, South Africa's linefishery was declared to be in a state of emergency, and commercial fishing effort was consequently reduced by 70%. A subsequent increase in stock biomass and intraspecific competition, coupled with environmental changes, were hypothesised to have thereafter altered the growth rate of hottentot, from 2000 to 2010. This study aimed to revise outdated age–growth models for the hottentot by using modern techniques (sectioned otoliths), and to compare age–growth relationships before and after the declared linefish state of emergency. The maximum age observed was 19 years, with no difference in the growth rate between sexes (p = 0.39–0.43) or time-periods (p = 0.96). Although the growth rate did not change, there is evidence that the age structure of the stock changed between time-periods as a result of changes in fishing pressure between 2000 and 2010. The enhanced recent growth model for hottentot, described as L_t = 418.063 (1 – e^{?0.104(t – [?4.709])}) (pooled sexes; n = 206), indicates a considerably slower growth rate for this species than was proposed previously using whole otoliths and has major implications for effective stock management.     

Relationships between air mass properties and mesoscale rainfall in New Zealand's Southern Alps

This paper identifies relationships between air mass properties and mesoscale rainfall when moist air blows over New Zealand's Southern Alps from the Tasman Sea. Around 50% of the variance in six-hourly rain volumes summed across three separate cross-mountain raingauge transects and in six-hourly rain volume spilling across the alpine divide are statistically explained by the following properties of the approaching air mass: relative humidity, wind velocity normal to the mountains, air mass stability and synoptically induced upward motion. These factors also explain about 25% (r≈0.5) of the variance in the downwind distance reached by the spillover rainfall. For the highest 10% of six-hourly rainfalls, spillover distance and magnitude are negatively correlated with the 700 or 500 hPa temperature. Multiple linear regression equations suitable for predicting rainfall intensity and spillover are developed. A progression is described in the magnitude and depth of vertical motion and resulting condensation rates over the mountains as the properties of the incoming air mass evolve through a storm. These changes, together with greater downwind advection of ice particles compared to raindrops, explain the observed statistical relationships between the air mass properties and mountain rainfall.     

Inclined K–Ar illite age spectra in brittle fault gouges: effects of fault reactivation and wall‐rock contamination

K–Ar clay fraction ages of brittle faults often vary with grain size, decreasing in the finer size fractions, producing an inclined age–grain‐size spectrum. K–Ar ages and mineralogical characterization of gouges from two normal faults in the Kongsberg silver mines, southern Norway, suggest that inclined spectra derived from brittle fault rocks reflect the mixing of inherited components with authigenic mineral phases. The ages of the coarsest and finest fractions constrain faulting at c. 260–270 Ma and reactivation around 200–210 Ma, respectively. This study demonstrates how wall‐rock contamination influences the K–Ar age of the coarsest size fractions and that authigenic illite and K‐feldspar can crystallize synkinematically under equivalent conditions and thus yield the same K–Ar ages.     

Surfactant and irrigation effects on wettable soils: runoff,erosion, and water retention responses

Surfactants are chemical compounds that can change the contact angle of a water drop on solid surfaces and are commonly used to increase infiltration into water repellent soil. Since production fields with water repellent soil often contain areas of wettable soil, surfactants applied to such fields worldwide will likely be applied to wettable soil, with unknown consequences for irrigation‐induced erosion, runoff, or soil water relations. We evaluated surfactant and simulated sprinkler irrigation effects on these responses for three wettable, Pacific Northwest soils, Latahco and Rad silt loams, and Quincy sand. Along with an untreated control, we studied three surfactants: an alkyl polyglycoside (APG) in solution at a concentration of 18 g active ingredient (AI) kg^?1, a block copolymer at 26 g kg^?1, and a blend of the two at 43 g kg^?1. From 2005 to 2009 in the laboratory, each surfactant was sprayed at a rate of 46·8 l ha^?1 onto each soil packed by tamping into 1·2‐ by 1·5‐m steel boxes. Thereafter, each treated soil was irrigated twice at 88 mm h^?1 with surfactant‐free well water. After each irrigation, runoff and sediment loss were measured and soil samples were collected. While measured properties differed among soils and irrigations, surfactants had no effect on runoff, sediment loss, splash loss, or tension infiltration, compared to the control. Across all soils, however, the APG increased volumetric water contents by about 3% (significant at p≤0·08) at matric potentials from 0 to ? 20 kPa compared to the control. With a decrease in the liquid–solid contact angle on treated soil surfaces, surfactant‐free water appeared able to enter, and be retained in pores with diameters ≥ 15 µm. All told, surfactants applied at economic rates to these wettable Pacific Northwest soils posed little risk of increasing either runoff or erosion or harming soil water relations. Moreover, by increasing water retention at high potentials, surfactants applied to wettable soils may allow water containing pesticides or other agricultural chemicals to better penetrate soil pores, thereby increasing the efficacy of the co‐applied materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Jurassic planktonic foraminifera from the United Kingdom

Unequivocal planktonic foraminifera have been discovered in Oxfordian strata from Dorset and Scotland. These assemblages are, in part, coeval with previously reported occurrences of planktonic taxa in the Oxfordian of Normandy and Seine Maritime (France). Three species are now reported from the United Kingdom for the first time: Globuligerina oxfordiana ( Grigelis, 1958 ), Haeuslerina helvetojurassica ( Haeusler, 1881 ) and Compactogerina sp. cf. C. stellapolaris ( Grigelis, 1977 ). There appears to be a close relationship between the distribution of these planktonic taxa in the UK and a marked sea-level highstand.     

Monte Carlo simulation of pair creation using petawatt lasers

Irradiating high-Z targets such as gold with ultra-intense lasers creates electron-positron pairs. In particular, the positron density in the plasma created by this procedure is higher than that obtained via other laboratory-based methods, with theoretical maximum densities exceeding 10¹⁸ cm⁻³. All of the significantly contributing processes are well-known and hence we can study this phenomenon using Monte Carlo simulation. We focus on the latter part of this procedure, the passage of high-energy electrons through the target creating pairs. In particular, we discuss the usefulness of CERN’s GEANT4 Monte Carlo code in simulating this process. Once this code is successfully calibrated, we will use it to perform parameter studies, and design future targets to optimize the positron yield.