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.     

Pc1-2 Discrete regular daytime pulsation bursts at high latitudes

A family of related Pc1-2 (0.2–10 s) discrete daytime geomagnetic pulsations is presented using pulsation data obtained at Davis, Antarctica, a typical polar-cap station. The morphological properties of IPRP and Pclb pulsation regimes, which maximize in amplitude and frequency of occurrence under the projection of the polar cusp, are examined. Furthermore, two other variations of discrete pulsation bursts yet to be named are also presented, viz IPFP (Intervals of Pulsations with Falling Period) and IPAP (Intervals of Pulsations with Alternating Period) which are observed on rare occasions. It is also suggested that the Pc1b (0.2–5 s) should be extended to incorporate Pc2b (5–10 s) which from the results in this paper are physically the same phenomenon and could be collectively classified as IPCP (Intervals of Pulsations with Constant Period).     

Ice‐cover variability on shallow lakes at high latitudes: model simulations and observations

A one‐dimensional thermodynamic model for simulating lake‐ice phenology is presented and evaluated. The model can be driven with observed daily or hourly atmospheric forcing of air temperature, relative humidity, wind speed, cloud amount and snowfall. In addition to computing the energy balance components, key model output includes the temperature profile at an arbitrary number of levels within the ice/snow (or the water temperature if there is no ice) and ice thickness (clear ice and snow‐ice) on a daily basis, as well as freeze‐up and break‐up dates. The lake‐ice model is used to simulate ice‐growth processes on shallow lakes in arctic, sub‐arctic, and high‐boreal forest environments. Model output is compared with field and remote sensing observations gathered over several ice seasons. Simulated ice thickness, including snow‐ice formation, compares favourably with field measurements. Ice‐on and ice‐off dates are also well simulated when compared with field and satellite observations, with a mean absolute difference of 2 days. Model simulations and observations illustrate the key role that snow cover plays on the seasonal evolution of ice thickness and the timing of spring break‐up. It is also shown that lake morphometry, depth in particular, is a determinant of ice‐off dates for shallow lakes at high latitudes. Copyright © 2003 John Wiley & Sons, Ltd.     

New Developments in Water Efficiency

1Water LossInitiativesUnaccounted-for water(or unbilled water)has beenreceiving newscrutiny at both the state and nationallevels.For years,water conservationeffortsin Europehave emphasized reduction in water loss to a muchgreater extent thaninthe United S…     

Europan surface phenomena

The interaction of corotating iogenic plasma with the surface of Europa in light of recent ice sputtering, experimental results, and published Voyager data has been examined. It has been found that the residual atmosphere of Europa is made up of sputtered molecular oxygen and is exospheric from the surface outwards. It was also found that if sputtering, redistribution, and escape are considered and the sulfur dioxide/water mixing ratio is held constant over a UV observing depth, the observed sulfur dioxide density on the trailing hemisphere lends support to the hypothesis that liquid water from the interior of Europa is boiling out and being deposited as a frost layer on the surface at the rate of about 0.04 μm/year.     

Anoxic nitrification: Evidence from Humber Estuary sediments (UK)

Conventional understanding of the nitrogen cycle in marine sediments has changed in recent years with the discovery of an alternative pathway for ammonia oxidation via the reduction of manganese oxides (during anoxic nitrification). In anoxic sediments, the potential for manganese oxides to serve as oxidant for nitrification may be considerable yet previous work on manganese-rich sediments has suggested anoxic nitrification may not be significant. In this study, the potential for anoxic nitrification in a range of sediment types was investigated. Laboratory incubation of sediment from three sites on the Humber Estuary, a microbially diverse environment, showed anoxic accumulation of nitrate, nitrite and dinitrogen gas, with and without the addition of synthetic manganese oxides. Incubation experiments confirmed anoxic nitrification as microbially mediated, with heat-killed controls yielding negative results. The anoxic nitrification reaction significantly depleted ammonia concentrations, and occurred simultaneously with manganese-, iron- and sulphate reduction, and methanogenesis. Taken in conjunction with other studies, results suggest anoxic nitrification may not only be dependent on total manganese concentrations but on manganese dynamics. Anoxic nitrification may be explained as a non-steady state reaction, dependent on the recent stability of a sediment system. Physical perturbation of sediments may cause the redistribution and/or introduction of manganese oxides and promote anoxic nitrification. The significance and persistence of anoxic nitrification is likely to depend on the frequency and magnitude of sediment perturbation, which explains why the reaction varies so widely across studied sites, and why it may not occur in some manganese-rich sediment.     

Phthalic acid complexation and the dissolution of forsteritic glass studied via in situ FTIR and X-ray scattering

Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t^1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10⁻⁶ cm² s⁻¹ in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10⁻¹² mol cm⁻² s⁻¹ (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm⁻³ to 2.2 g cm⁻³, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.     

Tracing groundwater flow and sources of organic carbon in sandstone aquifers using fluorescence properties of dissolved organic matter (DOM)

The fluorescence properties of groundwaters from sites in two UK aquifers, the Penrith Sandstone of Cumbria and the Sherwood Sandstone of South Yorkshire, were investigated using excitation–emission matrix (EEM) fluorescence spectroscopy. Both aquifers are regionally important sources of public supply water and are locally impacted by pollution. The Penrith Sandstone site is in a rural setting while the Sherwood Sandstone site is in suburban Doncaster. Fluorescence analysis of samples from discrete sample depths in the Penrith Sandstone shows decreasing fulvic-like intensities with depth and also shows a good correlation with CFC-12, an anthropogenic groundwater tracer. Tryptophan-like fluorescence centres in the depth profile may also provide evidence of rapid routing of relatively recent applications of organic slurry along fractures. Fluorescence analysis of groundwater sampled from multi-level piezometers installed within the Sherwood Sandstone aquifer also shows regions of tryptophan-like and relatively higher fulvic-like signatures. The fluorescence intensity profile in the piezometers shows tryptophan-like peaks at depths in excess of 50 m and mirrors the pattern exhibited by microbial species and CFCs highlighting the deep and rapid penetration of modern recharge due to rapid fracture flow. Fluorescence analysis has allowed the rapid assessment of different types and relative abundances of dissolved organic matter (DOM), and the fingerprinting of different sources of organic C within the groundwater system. The tryptophan:fulvic ratios found in the Penrith Sandstone were found to be between 0.5 and 3.0 and are characteristic of ratios from sheep waste sources. The Sherwood Sandstone has the lowest ratios (0.2–0.4) indicating a different source of DOM, most likely a mixture of terrestrial and microbial sources, although there is little evidence of pollution from leaking urban sewage systems. Results from these two studies suggest that intrinsic fluorescence may be used as a proxy for, or complementary tool to, other groundwater investigation methods in helping provide a conceptual model of groundwater flow and identifying different sources of DOM within the groundwater system.     

Acute toxicity of bromochlorinated seawater to selected estuarine species with a comparison to chlorinated seawater toxicity

The acute toxicity of bromochlorinated estuarine water (ca. 20%) was determined for several estuarine organisms. The most sensitive species were oysters (Crassostrea virginica, larvae and juveniles) and copepods (Acartia tonsa) with 48-h LC₅₀'s of 0·10 to 0·21 mg BrCl/litre. Palaemonetes pugio was most tolerant with a 96-h LC₅₀ of 0·70 mg BrCl/litre. The fish species tested (Menidia menidia, Brevoortia tyrannus and Leiostomus xanthurus) all had a 96-h LC₅₀ of 0·21–0·23 mg BrCl/litre.The BrCl toxicity data are compared with Cl₂ toxicity data for the same species. When the LC₅₀'s are expressed as equivalents per litre, BrCl is found to be two to four times less toxic than Cl₂. The ranking of species in terms of sensitivity is the same for both disinfectants.Some data are provided concerning the decay rates of BrCl and Cl₂ in estuarine water. BrCl was found to decay more rapidly than Cl₂ at higher ammonia levels (0·25 mg NH₄-N/litre). The question of chemical speciation is discussed with particular reference to the differential toxicities.