Surface complexation modeling of Yb(III) sorption and desorption on hematite and alumina

Sorption and desorption of Yb(III) were studied on hematite and on alumina using a surface complexation model. The experimental methodology was conceived to allow an analysis of the data using a constant capacitance model. The FITEQL code was used for the calculations.The experimental results tend to show reversibility of sorption when the surface loading is small, and irreversibility when the surface loading is high. Surface complexation modeling gives a good interpretation of these two phenomena, taking into account hydroxylation of the surface complexes. In these two cases, it is possible to describe sorption and desorption curves with the same surface stoichiometries and the same surface complexation constants. The existence of these surface complexes depends on the pH of the solution, surface loading, and reaction direction.     

Intercomparison between TRIO-EF and IMPACT codes with reference to experimental strontium migration data

This work presents an intercomparison exercise between two geochemical migration codes, TRIO-EF (an object-oriented finite element code) and IMPACT (a chemical engineering code using mixing cells in series). The predictions of the two codes are compared with the reference experimental results obtained in a previous study of strontium transport in soil columns. This simulated geochemical system is well documented and includes ion exchange and dissolution-precipitation reactions. The solution transport is simulated by a one-dimensional advection-dispersion model. The predictions of TRIO-EF and IMPACT are both in good agreement with the experimental results. However, slight differences can be observed between the two codes, especially when concentration discontinuities are involved, such as precipitation fronts or changes in boundary conditions. These discrepancies between the two codes can mainly be attributed to the different discretisation approaches.     

Fractionation of fulvic acids: characteristics and complexation with copper

Two fulvic acid samples isolated from Suwannee river (International Humic Substance Society) and Feeitsuey reservoir were subjected to gel filtration chromatography (GFC) for molecular size fractionation. The GFC-eluted samples were separated into three groups corresponding to the molecular weight ranges: < 220, 220-1000, and 1000-4000. Fluorescence quenching techniques were employed for determining the conditional stability coefficient and kinetic parameters of copper complexation with the three fractions of fulvic acids. Experimental conditions were pH 6, 5 x 10(-5)m total copper and 5 mg C litre(-1) of fulvic acids. The conditional stability coefficients of the fulvic acid fractions were in the order of 0.9-3.3 x 10(5)m(-1), and the forward and reverse rate constants were in the order of 6.9-12.4 x 10(3)m(-1) s(-1) and 3.5-8.0 x 10(-2) s(-1). Information could be useful in modelling copper transport in the hydrosphere.     

Linear least squares method for time series analysis with an application to a methane time series

A simple method of time series analysis, based upon linear least squares curve fitting, is developed. The method's advantages and disadvantages are discussed, and an example is presented using the Vostok Core methane record.     

NLEAP model simulation of climate and management effects on N leaching for corn grown on sandy soil

The Nitrate Leaching and Economic Analysis Package (NLEAP) model was used to evaluate effects of climate and N fertility on nitrate leaching from a 3-yr field experiment of continuous corn (Zea mays L.). Half of the plots were randomly chosen to be either nonirrigated or irrigated (based upon calculated potential evapotranspiration). Three replications of nitrogen (N) fertility (56, 112 and 224 kg ha⁻¹) were used. Soil was a Hecla sandy loam to loamy sand (Pachic Udic Haploboroll). Soil and climate data were from the upper Midwest U.S.A. database for NLEAP. On-site data were used in the model when available.This study shows that NLEAP is capable of integrating data collected for nonirrigated and irrigated conditions on sandy soil for a wide range of N treatments and predicting the nitrate available for leaching (NAL). Precipitation distribution and amount were different in each year. Calculated NAL provided an excellent indicator of potential nitrate leaching hazard. NLEAP output showed that leaching of residual N on this sandy soil is very sensitive to early-spring precipitation. The NLEAP model provided valuable insights concerning effects of climate and N and irrigation management on N leaching. To obtain optimum yields while minimizing nitrate leaching, this study indicates the need to use soil and plant-tissue testing, post-emergence N-fertilizer application, and modem irrigation-scheduling technology. Also, use of the NLEAP model along with field-plot experiments provide additional important information concerning timing of N-leaching events relative to climate and an additional assessment of the effectiveness of fertilizer-N management decisions.     

Radium-226 in cattails, Typha latifolia, and bone of muskrat, Ondatra zibethica (L.), from a watershed with uranium tailings near the city of Elliot Lake, Canada

Radium-226 concentrations were measured in the main food plants (cattails, Typha latifolia) and bone of adult muskrats (Ondatra zibethica (L.)), taken from a study area near Quirke Lake in the Serpent River drainage basin. This watershed receives drainage containing radionuclides from the U tailings near the City of Elliot Lake, Ontario, Canada. Two control sites (one local, one 130 km distant) were also sampled. Radium-226 levels in cattails varied by plant part and place of collection. Roots sampled in the study area had the highest mean (226)Ra level (1135.0 mBq g(-1)), stems and leaves had 284.2 and 275.9 mBq g(-1), respectively (dry-weight basis, n = 6 in all cases). Local and distant control cattails carried much lower (226)Ra levels (20.2 and 15.2 mBq g(-1) dry weight, respectively, using pooled equal portions of all plant parts, n = 3 in both cases). Muskrats from waters with mean total (226)Ra levels in the period, 1984-1987 greater than 75.0 mBq litre(-1) ('study-high' sites), near U tailings within 10 km of Quirke Lake, had a mean (geometric) bone level of (226)Ra of 344.9 mBq g(-1) (dry-weight basis, n = 36); those from nearby waters, containing < 75.0 mBq litre(-1) of (226)Ra ('study-low' sites), had a mean bone level (80.3 mBq g(-1), n = 9) similar to animals taken in unaffected local control areas 20 km from the tailings (79.1 mBq g(-1), n = 12); animals from the distant control area, near Sudbury, Ontario, had the lowest mean burden (11.5 mBq g(-1), n = 24). Levels were unrelated to age or sex of the animals. Dry-weight based (226)Ra concentration ratios (bone concentration/plant tissue concentration) were calculated to range from 0.3-1.4 in the study-high area to 2.4-6.3 in the local control area. Wet-weight based concentration ratios were about 4.3 times higher. Concentration ratios were similar to values calculated for other species and in general agreement with values calculated for humans. The muskrat is judged to be a useful indicator (biomonitor) of environmental (226)Ra levels as there is a highly significant positive correlation coefficient (r = 0.74) between bone and ambient (water) concentrations of the radionuclide (F79 = 95.04, P < 0.0001) Estimated yearly (226)Ra intake by people eating muskrats was calculated to be below the current allowable level set by Canadian regulatory authorities.     

U- and Th-series radionuclides in snowshoe hare (Lepus americanus) taken near U mill tailings close to Elliot Lake, Ontario, Canada

Snowshoe hare (Lepus americanus) trapped near U tailings had higher concentrations of (226)Ra in their bones (250 +/- 94 mBq g(-1) dry wt) than those from local control sites 3-15 km from the tailings (20-30 mBq g(-1) dry wt) and those from a distant control site 880 km away from the U mining area, which were below the detection limit (DL) (3.7 mBq g(-1) dry wt). Most chyme (stomach content) samples contained 226Ra below DL. Concentration ratios of 226Ra from tissues of local plants, considered important in the hare's diet, to bone ranged from 0.22 to 8.60. Concentrations of 210Pb and 210Po (95-245 mBq g(-1) dry wt) were not significantly different among tailings and control site populations. Disequilibrium between these isotopes and their precursors was noted. No significant accumulation of U and Th was noted at any site. Higher concentrations of 228Th compared to 232Th are attributed to accumulation of 228Ra in a manner similar to that of 226Ra. Based on bone 226Ra and 210Po contents, the maximum internal dose rates to the skeleton and the maximum life-time dose of hare living near tailings were 3.9 x 10(-5) Gy d(-1) and 4.2 x 10(-2) Gy, respectively. These rates were below the threshold required to produce osteosarcoma in other mammals and were considered unlikely to adversely affect hare during their lifetime. Radionuclide uptake by the animals was concluded to have no environmental significance in the transport of radionuclides from tailings to other locations.     

Effects of the phenylurea herbicide isoproturon on periphytic diatom communities in freshwater indoor microcosms

The toxic effects of the phenylurea herbicide Isoproturon -IPU: (3-(4-isopropylphenyl)-1, 1-dimethylurea)-were studied on the colonization of periphytic diatom communities, within indoor microcosms consisting of a mixed biotope (water column and natural sediment) and two biological species-rooted macrophyte cuttings (Elodea densa) and benthic bivalve molluscs (Corbicula fluminea). The periphyton, essentially composed of diatoms, was collected on artificial substrata (glass slides) in the upper layers of the water column, after two periods of exposure (34 and 71 days). IPU was initially added in the water or in the sediment compartment, at two nominal concentrations (L1 and L2 levels) for each contamination source-5 and 20 microg litre(-1) and 100 and 400 microg kg(-1) in sediment (w/w) respectively. The effects of IPU on the density and community structure of periphytic diatoms are described. A marked reduction in the diatom density was observed after 34 days exposure to the lower concentration of IPU in the water (5 microg litre(-1)). For the L2 levels, the very small number of live cells present did not permit quantification of the diatom density. After 71 days, recovery in community parameters occurred for the two contamination levels of the sediment and water column sources. Samples collected in the experimental units contaminated with the L2 levels were dominated by heterotrophic and smaller diatom species, such as Sellaphora seminulum. Data treatment based on factorial discriminant analysis enabled us to distinguish the different contamination conditions, with only 11 species from the 130 taxa identified.