Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO₃ electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (⁶⁵Cu/⁶³Cu) and Zn (⁶⁶Zn/⁶⁴Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (α_soln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δ_soln-solid) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).     

Response of xenotime to prograde metamorphism

Xenotime is a widespread accessory mineral in lower greenschist to upper amphibolite facies metasedimentary rocks from the Palaeoproterozoic Mount Barren Group, southwestern Australia. Xenotime is closely associated with detrital zircon, commonly forming syntaxial outgrowths, in samples of sandstone, micaceous quartzite, slate, phyllite, garnet-bearing semi-pelites, and in kyanite-, garnet-, and staurolite-bearing mica schists. In situ geochronology of xenotime from lower greenschist sandstones has previously yielded multiple U–Pb ages with peaks at ~2.0, ~1.7, and ~1.65 Ga, interpreted to represent the age of detritus, early diagenesis, and a later thermal event, respectively. New U–Pb dating of xenotime in slate yields a major population at ~1.7 Ga with a minor population at ~1.2 Ga, reflecting diagenetic and metamorphic growth, respectively, whereas xenotime in phyllite forms a minor age population at ~1.7 Ga and a main peak at ~1.2 Ga. Mid-greenschist facies semi-pelitic schists (quartz-muscovite-garnet) contain xenotime that formed before 1.8 Ga and at 1.2 Ga, representing detrital and peak metamorphic ages, respectively. Xenotime in samples of amphibolite facies schist (650°C and ~8 kbars) yields U–Pb ages of ~1.2 Ga, coinciding with the time of peak metamorphism. A single analysis of a xenotime core from an amphibolite facies schist gave an age of ~1.8 Ga, consistent with the presence of detrital xenotime. Our results suggest that detrital xenotime may be preserved under greenschist facies conditions, but is largely replaced during upper amphibolite facies conditions. Detrital xenotime is replaced through dissolution–reprecipitation reactions forming compositionally distinct rims during greenschist and amphibolite facies metamorphism at 1.2 Ga. Diagenetic xenotime is present in lower greenschist facies samples, but was not observed in metasedimentary rocks that had experienced temperatures above mid-greenschist facies metamorphism (450°C). The apparent disappearance of detrital and diagenetic xenotime and appearance of metamorphic xenotime during prograde metamorphism indicates that some of the yttrium, heavy rare earth elements, and phosphorus needed for metamorphic xenotime growth are probably derived from the replacement of detrital and diagenetic xenotime.     

Determination of the Rare-Earth Elements and Yttrium In 37 International Silicate Reference Materials By Inductively Coupled Plasma-Atomic Emission Spectrometry

The rare-earth elements (REE) and yttrium have been determined in 37 international rock and mineral reference materials. Samples were prepared using conventional rock-dissolution techniques, and the REE and yttrium were separated from the other constituents using cation-exchange chromatography. The REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) and yttrium were determined simultaneously by inductively coupled plasma-atomic emission spectrometry (ICP-AES). Results for four well-characterised USGS standard rocks agree favourably with "recommended" values and with REE determinations made previously by workers using ICP-AES, isotope dilution mass spectrometry, instrumental neutron activaton analysis and X-ray fluorescence spectrometry.
Les éléments de terres rares (TR) et yttrium ont été dosés dans 37 échantillons internationaux de réféence. Les échantillons ont été décomposés par dissolution acide et les TR séparés par résine échangeuse de cations. Les TR (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb, Lu) et yttrium ont été dosés simultanément par la spectrométrie d'émission-plasma inductif. Les résultats obtenus pour quatre échantillons de référence bien charactérisés de I'USGS se comparent favorablement avec ceux obtenus par la spectrométrie d'émission-plasma, la dilution isotopique, I'activation neutronique et par la spectrométrie d'é fluorescence-X.     

Are Urban-Canopy Velocity Profiles Exponential?

Using analyses of data from extant direct numerical simulations and large-eddy simulations of boundary-layer and channel flows over and within urban-type canopies, sectional drag forces, Reynolds and dispersive shear stresses are examined for a range of roughness densities. Using the spatially-averaged mean velocity profiles these quantities allow deduction of the canopy mixing length and sectional drag coefficient. It is shown that the common assumptions about the behaviour of these quantities, needed to produce an analytical model for the canopy velocity profile, are usually invalid, in contrast to what is found in typical vegetative (e.g. forest) canopies. The consequence is that an exponential shape of the spatially-averaged mean velocity profile within the canopy cannot normally be expected, as indeed the data demonstrate. Nonetheless, recent canopy models that allow prediction of the roughness length appropriate for the inertial layer’s logarithmic profile above the canopy do not seem to depend crucially on their (invalid) assumption of an exponential profile within the canopy.     

The effect of Doppler correction on measures of storm track intensity

In climate research, the intensity of a storm track is often measured by the band pass filtered eddy kinetic energy, geopotential variance or related variables. The interpretation of such fields disregards the influence the advection speed might have on these measures. In this paper the need for a Doppler corrected storm track measure is discussed. A Doppler corrected measure is defined and applied to 10 years of ECMWF reanalysis data, correcting the storm track measure for spatial and temporal variability of the advection speed. The storm track intensity is also calculated correcting only for the temporal variability of the advection speed. It is also related to fluctuations of the NAO teleconnection pattern. The Doppler correction suggests that (1) maximum and minimum baroclinic activity is found somewhat downstream of the locations indicated by non-corrected measures, (2) the storm track activity estimated by conventional measures is much too low in the areas of the eastern ends of the storm tracks, (3) the monthly mean time series of the strength of a storm track, as estimated by conventional measures, is strongly influenced by the variability of the advection speed at times, (4) the strength of the storm track seems to be less strongly connected with teleconnection patterns such as NAO or with the background mean flow speed than usually thought on the basis of conventional Eulerian statistics.     

Spatially explicit modelling of the impact of climate changes on pasture production in the North Island,New Zealand

To assess the potential impact of climate changes on pasture production in the North Island, New Zealand, eight climate scenarios of increased temperature and increased (or decreased) rainfall were investigated by integrating a polynomial regression model for pasture production with a Geographic Information System (GIS). The results indicated that the climate change scenarios assuming an increase in temperature by 1–2°C and a rainfall change by −20 to +20% would have a very significant impact on pasture production with a predicted pasture production variation from −46.2 to +51.9% compared with the normal climate from 1961–1990. Increased temperature would generally have a positive effect on pasture production in the south and southeast of the North Island, and increased rainfall would have a positive effect in the central, south and southeast of the North Island and a negative effect in the north of the North Island. The interaction of decreased rainfall and increased temperature would have a negative impact for the whole North Island except some central areas with high rainfall. Relevant management practices for coping with potential climate change are discussed.     

Near Wall Flow over Urban-like Roughness

In this study, comprehensive measurements over a number of urban-type surfaces with the same area density of 25% have been performed in a wind tunnel. The experiments were conducted at a free stream velocity of 10 m s^-1 and the main instrumentation was 120 ° x-wire anemometry, but measurement accuracy was checked using laser Doppler anemometry.The results haveconfirmed the strong three-dimensionalityof the turbulent flow inthe roughness sublayer and the depths of the inertial sublayer (log-law region) and roughness sublayer for each surface have been determined. Spatial averaging has been used to remove the variability of the flow in the roughness sublayer due to individual obstacles and it is shown that the spatially averaged mean velocity in the inertial sublayer and roughness sublayer can,together, be described by a single log-law with a mean zero-plane displacement and roughness length for the surface, provided that the proper surface stress is known. The spatially averaged shear stresses in the inertial sublayer and roughness sublayer are compared with the surface stress deduced from form drag measurements on the roughness elements themselves.The dispersive stress arising from the spatial inhomogeneity in the mean flow profiles was deduced from the data and is shown to be negligible compared with the usual Reynolds stresses in the roughness sublayer. Comparisons have been made between a homogeneous (regular element array) surface and one consisting of random height elements of the same total volume. Although the upper limits of the inertial sublayer for both surfaces were almost identical at equivalent fetch, the roughness sublayer was much thicker for the random surface than for the uniform surface, the friction velocity and the roughness length were significantly larger and the `roughness efficiency' was greater. It is argued that the inertial sublayer may not exist at all in some of the more extreme rough urban areas. These results will provide fundamental information for modelling urban air quality and forecasting urban wind climates.     

Scalar Fluxes Near a Tall Building in an Aligned Array of Rectangular Buildings

Scalar dispersion from ground-level sources in arrays of buildings is investigated using wind-tunnel measurements and large-eddy simulation (LES). An array of uniform-height buildings of equal dimensions and an array with an additional single tall building (wind tunnel) or a periodically repeated tall building (LES) are considered. The buildings in the array are aligned and form long streets. The sensitivity of the dispersion pattern to small changes in wind direction is demonstrated. Vertical scalar fluxes are decomposed into the advective and turbulent parts and the influences of wind direction and of the presence of the tall building on the scalar flux components are evaluated. In the uniform-height array turbulent scalar fluxes are dominant, whereas the tall building produces an increase of the magnitude of advective scalar fluxes that yields the largest component. The presence of the tall building causes either an increase or a decrease to the total vertical scalar flux depending on the position of the source with respect to the tall building. The results of the simulations can be used to develop parametrizations for street-canyon dispersion models and enhance their capabilities in areas with tall buildings.     

Atmospheric effects from post-nuclear fires

During a large nuclear war, the atmosphere would be loaded with huge quantities of pollutants, which are produced by fires in urban and industrial centers, cultivated lands, forests and grasslands. Especially detrimental are the effects of light absorbing airborne particles. An analysis of the amounts of the various types of fuels which could burn in a nuclear war indicates that more than 10¹⁴ g of black smoke could be produced by fires started by the nuclear explosions. Due to this, the penetration of sunlight to the earth's surface would be reduced greatly over extended areas of the northern hemisphere, maybe even globally. This could temporarily cause extreme darkness in large areas in midlatitudes and reduce crop growth and biospheric productivity.This situation would last for several weeks and cause very anomalous meteorological conditions. Much solar radiation would be absorbed in the atmosphere instead of at the earth's surface. The land areas and lower atmosphere would, therefore, cool and the overlying atmosphere warm, creating strong vertical thermal stability in a highly polluted atmosphere. For extended periods and in large parts of the world, weather conditions would be abnormal. The resulting cold, probably freezing, temperatures at the ground would interfere severely with crop production during the growing season and cause extreme conditions for large sections of the biosphere. The combination of lack of sunlight, frost and other adverse meteorological conditions would add enormously to the already huge problems of the survivors.