Animal bones have been studied as a resource of low-crystalline apatite for immobilization of toxic heavy metals. Chemical and thermal treatments can be applied for selective removal of bone organic constituents. In this study, the impact of different treatment factors was determined by experimental design methodology, and comparison of the estimated effects was performed in order to optimize the treatment conditions. Fractional factorial design with five variables at two levels was applied for factors screening. The type of chemical reagent (H 2 O 2 or NaOH), its concentration (0.1 or 2 mol/L), reaction temperature (20 or 60°C), contact time (1 or 3 h) and sample annealing (without or at 400°C) were considered as process variables. Structural properties of bone sorbents, loss of ignition, point of zero charge, surface functional groups, specific surface area, chemical composition, and Cd 2? sorption efficiency, were selected as system responses. Samples significantly differed in respect to the organic phase content and composition, thus mechanisms of Cd 2? sorption were complex. Statistical analysis has revealed that, between all studied factors, temperature treatment was the most important for sorbents increased specific surface area, porosity and cation sorption. Furthermore, NaOH was more effective than H 2 O 2 , while the effects produced by variation of other factors were less pronounced. The highest proportion of bio-apatite with desired low crystallinity and high specific surface area was achieved by synergetic effects of chemical treatment with NaOH and thermal treatment at 400°C.
Sorption-desorption properties of cobalt(II) and strontium(II) ions were studied using a soil sample from the vicinity of the Serbian radioactive waste processing and interim storage facilities. The mobility of the cations in the soil was evaluated and compared with the intention to facilitate the selection of optimal remediation strategy in case of accidental soil contamination with radioactive cobalt-60 and strontium-90 isotopes. A systematic sorption study was performed through a series of batch experiments at different aging times, cation concentrations and pH. Kinetics experiments revealed that sorbed amounts of cobalt(II) continuously increased with contact time until quasi-equilibrium was reached, while initial fast strontium(II) sorption was followed by a desorption step. Based on the shapes of the sorption isotherms and calculated sorption parameters, it was concluded that cobalt(II) sorbed more selectively and strongly than strontium(II). Sequential extraction showed that, regardless of the initial content of contaminants in the soil and the aging time, high amounts of both cations were bonded to relatively mobile fractions: strontium(II) in the exchangeable, while cobalt(II) in the carbonate and ferromanganese oxide fraction. Strontium(II) was readily desorbed in acidic, calcium(II) and ethylenediaminetetraacetic acid-containing media, whereas complexing agents such as citric and tartaric acids at low pH were more effective reagents for cobalt(II) desorption. The results from the present study indicate that chemical extraction can be considered as remediation option for strontium(II)-and cobalt(II)-contaminated soil.
The removal of 60Co and 90Sr from the aqueous phase was tested using red mud - the fine grained residue from bauxite ore processing. This industrial waste represents a mixture of numerous minerals, mainly oxides and hydroxides of Fe, Al, Si, and Ti. Experiments were conducted as a function of contact time, pH, and pollutant concentrations. Kinetic data were well fitted with a pseudo-second order equation. The calculated rate constants and initial sorption rates indicated faster sorption of Sr2+ ions. Removal of both cations rapidly increased with the initial pH increase from 2.5 to 3.5. With the further increase of pH, Co2+ sorption was nearly constant (98%-100%), whereas Sr2+ removal remained at the same level to initial pH ~8 and gradually increased to 100% at pH 12. Equilibrium sorption data followed the Langmuir model, with the maximum sorption capacities of 0.52 mmol/g for Co2+ and 0.31 mmol/g for Sr2+. Sorbed cations exhibited high stability in distilled water. Desorption of Co2+ was also negligible in the presence of the competing Ca2+ cation, while 42%-25% of Sr2+ ions were desorbed depending on the previously sorbed amount. The results indicate that red mud is of potential significance as Co2+ and Sr2+ immobilization agent due to its high efficiency, abundance, and low-cost. [Projekat Ministarstva nauke Republike Srbije, br. 43009]
Bulk samples collected on a daily basis at three principal meteorological stations in central Serbia were analyzed on chloride (Cl(-)), nitrate (NO(3)(-)), sulfate (SO(4)(2-)), sodium (Na(+)), ammonium (NH(4)(+)), potassium (K(+)), calcium (Ca(2+)), and magnesium (Mg(2+)) in addition to precipitation amount, pH and conductivity measurements over the period 1998-2004. The data were subjected to variety of analyses (linear regression, principal component analysis, time series analysis) to characterize precipitation chemistry in the study area. The most abundant ion was SO(2-)(4) with annual volume weighted mean concentration of 242 microeq L(-1). Neutralization of precipitation acidity occurs both as a result of the dissolution of alkaline compounds containing Ca(2+), Mg(2+), and K(+) as well as the absorption of ammonia. The ratio of SO(4)(2-)/NO(3)(-) was above 5, which indicated that the combustion process of low-grade domestic lignite for electricity generation from coal-fired thermal power plants was the main source of pollution in the investigated area. A considerable mean annual bulk wet deposition of SO(4)-S determined by precipitation amount and concentrations of sulfate in the precipitation was calculated to be 12-35 kg ha(-1).
The prospects of rinsed red mud (alumina production residue) utilization for liquid radioactive waste treatment have been investigated, with Co(2+) and Sr(2+) as model cations of radioactive elements. To evaluate the sorption effectiveness and corresponding binding mechanisms, the process was analyzed in batch conditions, by varying experimental conditions (pH, Co(2+) and Sr(2+) concentrations in single solutions and binary mixtures, contact time, and the concentration of competing cations and ligands common in liquid radioactive waste). Comparison of the Co(2+) and Sr(2+) sorption pH edges with the red mud isoelectric point has revealed that Co(2+) removal took place at both positive and negative red mud surface, while Sr(2+) sorption abruptly increased when the surface became negatively charged. The increase of initial cation content and pH resulted in increased equilibrium times and sorption capacity and decreased rate constants. From single metal solutions and various binary mixtures, Co(2+) was sorbed more efficiently and selectively than Sr(2+). While Sr(2+) sorption was reduced by coexisting cations in the order Al(3+) ≥ Ca(2+) >Na(+) ≥Cs(+), removal of Co(2+) was affected by Al(3+) species and complexing agents (EDTA and citrate). Desorption of Co(2+) was negligible in Ca(2+) and Sr(2+) containing media and in solutions with initial pH 4-7. Sr(2+) desorption was generally more pronounced, especially at low pH and in the presence of Co(2+). Collected macroscopic data signify that Co(2+) sorption by red mud minerals occurred via strong chemical bonds, while Sr(2+) was retained mainly by weaker ion-exchange or electrostatic interactions. Results indicate that the rinsed red mud represent an efficient, low-cost sorbent for Co(2+) and Sr(2+) immobilization.
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