Maria Josefa Santos

Cadmium mobility in sediments and soils from a coal mining area on Tibagi River watershed: environmental risk assessment.

The risk of cadmium contamination in the Tibagi River watershed (Parana State, Brazil) affected by past coal mining activities was assessed through sorption-desorption modeling for sediment and soil samples. The acidic character of the samples resulted in more competition between the cadmium ions and protons, thereby influencing the cadmium sorption-desorption. The sorption isotherms were fitted to the Langmuir and Freundlich single models and to the dual-site Langmuir-Freundlich (or Sips) model. The single-site models indicated a low-energy character of sorption sites on the sample sorption sites, whereas the dual-site model explained the availability of higher-affinity and lower-affinity non-specific sites. The correlation of the sorption and desorption constants with the physicochemical and mineralogical characteristics of the samples showed that the cadmium sorption behavior was significantly affected by the pH, point of zero charge, and also by the magnesium, aluminum, calcium and manganese amounts. Besides, the desorption rate and hysteresis index suggested a high risk of cadmium mobilization along the Tibagi River basin.

Reversibility of La and Lu sorption onto smectites: Implications for the design of engineered barriers in deep geological repositories

The sorption reversibility of La and Lu (considered as actinide analogues) onto a set of smectites (bentonite FEBEX; hectorite, HEC; MX80; saponite, SAP; Otay montmorillonite, SCa-3; and Texas montmorillonite, STx-1) was studied to estimate actinide retention by smectites that are candidates for use as engineered barriers in deep geological repositories. The sorption distribution coefficients (K(d)) and the reversibility parameters (desorption distribution coefficients (K(d,des)), adjusted distribution coefficients (K(d,adj)), and desorption rates (R(des))) were determined from batch tests in two ionic media: deionized water and Ca 0.02 mol L(-1). The latter simulates possible conditions due to the presence of concrete leachates. The results varied greatly depending on the ionic medium, the lanthanide concentration and the clay structure. The high values of K(d,des) obtained (up to 1.1 x 10(5) and 9.2 x 10(4) L kg(-1) for La and Lu in water, and 2.8 x 10(4) and 4.1 x 10(4)L kg(-1) for La and Lu in the Ca medium) indicate the suitability of the tested smectites for lanthanide (and therefore, actinide) retention. Based on all the data, SCa-3, HEC and FEBEX clays are considered the best choices for water environments, whereas in Ca environments the suitable clays depended on the lanthanide considered.

Monte Carlo method applied to modeling copper transport in river sediments

Monte Carlo simulation (MCS) methodology has been applied to explain the variability of parameters for pollutant transport and fate modeling. In this study, the MCS method was used to evaluate the transport and fate of copper in the sediment of the Tibagi River sub-basin tributaries, Southern Brazil. The statistical distribution of the variables was described by a dataset obtained for copper concentration using sequential extraction, organic matter (OM) amount, and pH. The proposed stochastic spatial model for the copper transport in the river sediment was discussed and implemented by the MCS technique using the MatLab 7.3™ mathematical software tool. In order to test some hypotheses, the sediment and the water column in the river ecosystem were considered as compartments. The proposed stochastic spatial model makes it possible to predict copper mobility and associated risks as a function of the organic matter input into aquatic systems. The metal mobility can increase with the OM posing a rising environmental risk.

Examination of competitive lanthanide sorption onto smectites and its significance in the management of radioactive waste.

The competitive effect of La and Lu (analogues of radionuclides appearing in radioactive waste) in the sorption in four smectites was examined. Sorption and desorption distribution coefficients (K(d); K(d,des)), and desorption rates (R(des)) were determined from batch tests in two media: deionized water and, to consider the influence of cement leachates, 0.02 mol L(-1) Ca. The competitive effect was lower when high-affinity sites were available, as in the water medium at the lowest range of initial lanthanide concentration, with high K(d) for La and for Lu (5-63×10(4) L kg(-1)). Lower K(d) was measured at higher initial concentrations and in the Ca medium, where Lu showed a stronger competitive effect. This was confirmed by fitting the sorption data to a two-solute Langmuir isotherm. The desorption data indicated that sorption was virtually irreversible for the scenarios with high sorption, with an excellent correlation between K(d) and K(d,des) (R(2) around 0.9 for the two lanthanides). Assuming that radioactive waste is a mixture of radionuclides, and that Ca ions will be provided by the cement leachates, this would reduce the retention capacity of clay engineered barriers.

Sorption and desorption of silver ions by bentonite clays

Anthropogenic activities have increased the concentration of metal species in the environment. The toxicity of silver ions to aquatic and terrestrial organisms has required monitoring by analytical methods, besides actions to promote its control as pollutant. Sorption and desorption processes are directly related to the mobility and availability of metal ions in the environment. In this context, clay minerals can be used for pre-concentration, removal and recovery of silver ions from aqueous solution. Herein, two bentonite clays (BaVC-1 and SWy-2) were characterised and applied to investigate the sorption and desorption of silver ions. Isotherms were fitted to the dual-mode Langmuir-Freundlich model to qualify and quantify sorption sites and evaluate the mobilisation process. The maximum sorption capacity was 743 and 849 meq kg−1 for BaVC-1 and SWy-2, respectively. Hysteresis index (HI) and mobilisation factor (MF) suggest that the desorption of silver ions in BaVC-1 is about four times more conducive compared to that in SWy-2, although both materials have demonstrated a great potential for Ag+ pre-concentration from aqueous solutions.

Sorption-desorption of antimony species onto calcined hydrotalcite: surface structure and control of competitive anions

Calcined hydrotalcite can be applied to remove anionic contaminants from aqueous systems such as antimony species due to its great anion exchange capacity and high surface area. Hence, this study evaluated antimonite and antimonate sorption-desorption processes onto calcined hydrotalcite in the presence of nitrate, sulfate and phosphate. Sorption and desorption experiments of antimonite and antimonate were carried out in batch equilibrium and the post-sorption solids were analyzed by X-ray fluorescence (EDXRF). Sorption data were better fitted by dual-mode Langmuir-Freundlich model (R2>0.99) and desorption data by Langmuir model. High maximum sorption capacities were found for the calcined hydrotalcite, ranging from 617 to 790meqkg-1. The competing anions strongly affected the antimony sorption. EDXRF analysis and mathematical modelling showed that sulfate and phosphate presented higher effect on antimonite and antimonate sorption, respectively. High values for sorption efficiency (SE=99%) and sorption capacity were attributed to the sorbent small particles and the large surface area. Positive hysteresis indexes and low mobilization factors (MF>3%) suggest very low desorption capacity to antimony species from LDH. These calcined hydrotalcite characteristics are desirable for sorption of antimony species from aqueous solutions.