Assessment of alternative adsorption models and global sensitivity analysis to characterize hexavalent chromium loss from soil to surface runoff

We investigate our ability to assess transfer of hexavalent chromium, Cr(VI), from the soil to surface runoff by considering the effect of coupling diverse adsorption models with a two‐layer solute transfer model. Our analyses are grounded on a set of two experiments associated with soils characterized by diverse particle size distributions. Our study is motivated by the observation that Cr(VI) is receiving much attention for the assessment of environmental risks due to its high solubility, mobility, and toxicological significance. Adsorption of Cr(VI) is considered to be at equilibrium in the mixing layer under our experimental conditions. Four adsorption models, that is, the Langmuir, Freundlich, Temkin, and linear models, constitute our set of alternative (competing) mathematical formulations. Experimental results reveal that the soil samples characterized by the finest grain sizes are associated with the highest release of Cr(VI) to runoff. We compare the relative abilities of the four models to interpret experimental results through maximum likelihood model calibration and four model identification criteria (i.e., the Akaike information criteria [AIC and AIC_C] and the Bayesian and Kashyap information criteria). Our study results enable us to rank the tested models on the basis of a set of posterior weights assigned to each of them. A classical variance‐based global sensitivity analysis is then performed to assess the relative importance of the uncertain parameters associated with each of the models considered, within subregions of the parameter space. In this context, the modelling strategy resulting from coupling the Langmuir isotherm with a two‐layer solute transfer model is then evaluated as the most skilful for the overall interpretation of both sets of experiments. Our results document that (a) the depth of the mixing layer is the most influential factor for all models tested, with the exception of the Freundlich isotherm, and (b) the total sensitivity of the adsorption parameters varies in time, with a trend to increase as time progresses for all of the models. These results suggest that adsorption has a significant effect on the uncertainty associated with the release of Cr(VI) from the soil to the surface runoff component.     

Preparation,collisional decay and transfer of alignment in C2H2 21

Stimulated Raman scattering is used to prepare ensembles of aligned acetylene molecules in thev ₂=1 excited vibrational level. Decay and transfer of the alignment is followed by laser induced fluorescence. Measurements of the initially excited alignment agree well with theoretical calculations. The rate constants for decay decrease as the rotational quantum numberJ of the excited level increases.     

National flood discharge mapping in Austria

This article presents the approach and the results of a study in which 30, 100 and 200 year return period flood discharges were estimated for 26,000 km of Austrian streams. Three guiding principles were adopted: combination of automatic methods and manual assessments by hydrologists to allow speedy processing and account for the local hydrological situation; combination of various sources of information including flood peak samples, rainfall data, runoff coefficients and historical flood data; and involvement of the Hydrographic Services to increase the accuracy and enhance the acceptance of results. The flood discharges for ungauged catchments were estimated by the Top-kriging approach with manual adjustment to the local flood characteristics. The adopted combination approach proved to be very efficient both in terms of the project time required and in terms of the accuracy and acceptability of the estimated flood discharges of given return periods.     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.     

Multi-AUV Control and Adaptive Sampling in Monterey Bay

Operations with multiple autonomous underwater vehicles (AUVs) have a variety of underwater applications. For example, a coordinated group of vehicles with environmental sensors can perform adaptive ocean sampling at the appropriate spatial and temporal scales. We describe a methodology for cooperative control of multiple vehicles based on virtual bodies and artificial potentials (VBAP). This methodology allows for adaptable formation control and can be used for missions such as gradient climbing and feature tracking in an uncertain environment. We discuss our implementation on a fleet of autonomous underwater gliders and present results from sea trials in Monterey Bay in August, 2003. These at-sea demonstrations were performed as part of the Autonomous Ocean Sampling Network (AOSN) II project     

Multi-Scale Texture Modeling

Patterns of crystallographic preferred orientation are referred to as texture. The specific subject of texture analysis is the experimental determination and interpretation of the statistical distribution of orientations of crystals within a specimen of polycrystalline material, which could be metals or rocks. The objective is to relate an observed pattern of preferred orientation to its generating processes and vice versa. In geosciences, texture of minerals in rocks is used to infer constraints on their tectono-metamorphic history. Since most physical properties of crystals, such as elastic moduli, the coefficients of thermal expansion, or chemical resistance to etching depends on crystal symmetry and orientation, the presence of texture imparts directional properties to the polycrystalline material. A major issue of mathematical texture analysis is the resolution of the inverse problem to determine a reasonable orientation density function on SO(3) from measured pole intensities on , which relates to the inverse of the totally geodesic Radon transform. This communication introduces a wavelet approach into mathematical texture analysis. Wavelets on the two-dimensional sphere and on the rotational group SO(3) are discussed, and an algorithms for a wavelet decomposition on both domains following the ideas of Ta-Hsin Li is given. The relationship of these wavelets on both domains with respect to the totally geodesic Radon transform is investigated. In particular, it is shown that the Radon transform of these wavelets on SO(3) are again wavelets on . A novel algorithm for the inversion of experimental pole intensities to an orientation density function based on this relationship is developed.     

Geochemical and isotopic zoning patterns of plagioclase megacrysts in gabbroic dykes from the Gardar Province, South Greenland: implications for crystallisation processes in anorthositic magmas

Chemical and Sr isotopic zoning patterns in plagioclase megacrysts from gabbroic dykes in the Gardar Province can be used to elucidate magma-chamber and emplacement processes. The megacrysts occur either as single crystals or assembled as anorthosite xenoliths. The size of the megacrysts varies from <1 cm to 1 m. They consist of a large core with variable zonation (An_58-39) and a relatively small (<600 µm), normally zoned rim (An_62-27). The contact between core and rim is sharp and marked by a sharp increase in anorthite content which can reach 11 mol% An. This gap is interpreted as having formed during dyke emplacement due to a sudden pressure release. Some of the megacryst cores show a fairly constant composition whereas others exhibit an unusual wavy-oscillatory zoning which has not been reported elsewhere to our knowledge. The oscillatory zoning has wavelengths of up to 2,500 µm and a maximum amplitude of 7 mol% An. It is interpreted as reflecting movements of the crystals in the magma reservoir. The Sr isotopic composition of one crystal shows a radiogenic inner core ((⁸⁷Sr/⁸⁶Sr)_i=0.7044) and a less radiogenic outer core ((⁸⁷Sr/⁸⁶Sr)_i=0.7039-0.7036). The lack of a significant change between outer core and rim ((⁸⁷Sr/⁸⁶Sr)_i=0.7037) is consistent with formation of the more An-rich rim due to pressure release. Variations in the core may be related to movements of the crystal and/or magma mixing. A trace-element profile across a megacryst shows a small increase in Sr and small decreases in Ba and La contents of the recalculated melt composition across the core-rim boundary, whereas P, Ce, Nd and Eu remain constant. Melt compositional changes upon emplacement are therefore considered to be of minor importance. Constant ratios of incompatible trace elements in the megacryst cores indicate a dominant influence of a lower crustal source on trace-element budgets.     

Quantifying Arctic contributions to climate predictability in a regional coupled ocean-ice-atmosphere model

The relative importance of regional processes inside the Arctic climate system and the large scale atmospheric circulation for Arctic interannual climate variability has been estimated with the help of a regional Arctic coupled ocean-ice-atmosphere model. The study focuses on sea ice and surface climate during the 1980s and 1990s. Simulations agree reasonably well with observations. Correlations between the winter North Atlantic Oscillation index and the summer Arctic sea ice thickness and summer sea ice extent are found. Spread of sea ice extent within an ensemble of model runs can be associated with a surface pressure gradient between the Nordic Seas and the Kara Sea. Trends in the sea ice thickness field are widely significant and can formally be attributed to large scale forcing outside the Arctic model domain. Concerning predictability, results indicate that the variability generated by the external forcing is more important in most regions than the internally generated variability. However, both are in the same order of magnitude. Local areas such as the Northern Greenland coast together with Fram Straits and parts of the Greenland Sea show a strong importance of internally generated variability, which is associated with wind direction variability due to interaction with atmospheric dynamics on the Greenland ice sheet. High predictability of sea ice extent is supported by north-easterly winds from the Arctic Ocean to Scandinavia.     

Observations of the convective plume of a lake under cold-air advective conditions

Moderating effects of Lake Apopka, Florida on downwind surface temperatures were evaluated under cold-air advective conditions. Point temperature measurements north and south of the lake and data obtained from a thermal scanner flown at 1.6 km indicate that surface temperatures directly downwind may be higher than surrounding surface temperatures by as much as 5 °C under conditions of moderate winds (~4 m s^–1). No substantial temperature effects were observed with surface wind speed less than 1 m s^–1. Fluxes of sensible and latent heat from Lake Apopka were calculated from measurements of lake temperature, net radiation, relative humidity and air temperature above the lake. Bulk transfer coefficients and the Bowen ratio were calculated and found to be in agreement with reported data for non-advective conditions.IFAS Journal Series No. 1006.