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Abstract  

The kinetics of complexation (C) and decomplexation (D) reactions between Eu(III) and Aldrich humic acid (HA) was investigated as a function of pH (pH 4, 5, 6, 7 and 8) in the system Eu(III) - HA - Amberlite IR-120(Na) (I = 0.1). The derivation of the kinetic differential equations was based on the reactions of Eu3+ with, so called, strong (HAS) and weak (HAW) carboxylic groups of HA formulated in accordance with the new complexation model.1 The differential equations determining d[EuaHAS]/dt and d[EubHAW]/dt have the classical form applicable for reversible reactions where the forward reaction is the C-reaction and the reverse one is the D-reaction. Kinetic model used for the evaluation of experimental data includes these differential equations and the film diffusion model of sorption of Eu3+ on Amberlite IR-120(Na).

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Abstract  

Attapulgite has been applied in the sorption of metal and radionuclide ions since its discovery. Herein, radionuclide Am(III) sorption onto attapulgite was carried out at 25 °C in 0.01 mol/L NaNO3 solutions. Effects of contact time, Am(III) initial concentration, pH, humic acid and temperature on Am(III) sorption onto attapulgite were investigated. The sorption of Am(III) increases with increasing contact time and reaches a maximum value within 24 h at different Am(III) initial concentration. The fast sorption velocity indicates that strong chemical sorption or strong surface complexation contributes to the sorption of Am(III) onto attapulgite under the experimental conditions. The experimental data can be described well by the pseudo-second-order rate model. The sorption of Am(III) onto attapulgite is strongly dependent on pH values and surface complexation is the main sorption mechanism. The presence of HA enhances the sorption of Am(III) onto attapulgite at pH < 8.5, whereas, at pH > 8.5, little effect of HA on Am(III) sorption is observed. The Langmuir, Freundlich and D-R models were used to simulate the sorption data at different pH values and the results indicated that Langmuir model simulates the experimental data better than Freundlich and D-R models. The thermodynamic parameters indicates that the sorption of Am(III) onto attapulgite is an endothermic and spontaneous process. The results suggest that the attapulgite is a suitable material as an adsorbent for preconcentration and immobilization of Am(III) from aqueous solutions.

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Abstract  

Sorption of Th(IV) on Na-rectorite as a function of pH, ionic strength, soil humic acid (HA) and fulvic acid (FA) are studied under ambient conditions by using a batch technique. The results indicate that the sorption of Th(IV) on Na-rectorite is not only dependent on medium pH values, but also dependent on medium ionic strength and humic substances. Surface complexation and cation competition exchange account for Th(IV) sorption on Na-rectorite. The sorption of Th(IV) on Na-rectorite decreases with the increase on the concentration of NaNO3, Mg(NO3)2 and Ca(NO3)2, and increases with the increasing amount of HA/FA in the suspension/adsorbed on rectorite. Soil HA/FA enhances the sorption of Th(IV) on rectorite at medium pH<4 drastically, but the presence of FA reduces the sorption of Th(IV) at medium pH>6, and HA has no effect on Th(IV) sorption at medium pH>6. An interpretation for the results is attempted, considering the occurrence of different sorption mechanisms.

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Abstract  

The sorption of Eu(III) on calcareous soil as a function of pH, humic acid (HA), temperature and foreign ions was investigated under ambient conditions. Eu(III) sorption on soil was strongly pH dependent in the observed pH range. The effect of ionic strength was significant at pH < 7, and not obvious at pH > 8. The type of salt cation used had no visible influence on Eu(III) uptake on soil, however at low pH values, the influence of anions was following the order: Cl ≈ NO3  > ClO4 . In the presence of HA, the sorption edge obviously shifted about two pH units to the lower pH, whilst in range of pH 6–7, the sorption of Eu(III) decreased with increasing pH because a considerable amount of Eu(III) was present as humate complexes in aqueous phase, then increased again at pH > 11. The results indicated that the sorption of Eu(III) on soil mainly formed outer-sphere complexes and/or ion exchange below pH ~7; whereas inner-sphere complexes and precipitation of Eu(OH)3(s) may play main role above pH ~8.

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Abstract  

The bentonite from Gaomiaozi county (Inner Mongolia, China) (denoted as GMZ bentonite) was characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The effect of pH, contact time, ionic strength, humic acid (HA) and Eu(III) concentrations on Eu(III) sorption to the GMZ bentonite was studied by batch technique under ambient conditions. The sorption of Eu(III) on GMZ bentonite was strongly dependent on pH and independent of ionic strength. The sorption of Eu(III) on GMZ bentonite was mainly dominated by surface complexation rather than by ion exchange. The presence of HA enhanced Eu(III) sorption at low pH values, but decreased Eu(III) sorption at high pH values. The enhanced sorption of Eu(III) on GMZ bentonite at low pH was attributed to the strong complexation of Eu(III) with surface adsorbed HA on GMZ bentonite and the reduced sorption of Eu(III) at high pH was attributed to the formation of soluble HA–Eu complexes in aqueous solution. The strong sorption of Eu(III) on GMZ bentonite suggested that the GMZ bentonite could be used as the backfill material in nuclear waste disposal.

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Abstract  

The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations on the Co(II) sorption on γ-Al2O3 in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al2O3 in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly positive influence of HA at low pH on the Co(II) sorption on γ-Al2O3 was attributed to strong surface binding of HA on γ-Al2O3 and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO)xCo2−x. Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al2O3 in the presence of HA.

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Abstract  

Sorption of tracer Am3+ to silicate particles was studied as a function of pcH (4 to 9) and of ionic strength [0.20M to 1.50M (NaClO4)] at 298 K. The sorption increased with increased pcH from 4 to 6 above which saturation was observed. The insensitivity of Am3+ sorption to increased ionic strength indicates inner-sphere complexation with the surface silicate sites. The effects of different complexing anions such as carbonate, acetate, oxalate, phosphate, citrate, EDTA and humic acid, on Am3+ sorption were investigated. Synergistic enhancement in Am3+ sorption was observed in the presence of phosphate (4≤pcH≤7) and acetate (4≤pcH≤5) ligands at 0.20M NaClO4. The presence of the other ligands inhibited Am3+ sorption in the order: EDTA > citrate > oxalate > carbonate. Am3+ sorption in the presence of HA (25.00 mg/l) increased in the pcH range of 4.0 to 5.5, then decreased. Increased ionic strength enhanced Am3+ sorption in the presence of 25.00 mg/l HA for 4≤pcH≤9. The sorption increased in the presence of a mixture of HA (25.00 mg/l) and phosphate (1.00·10−3M) as compared to that of HA (25.00 mg/l) alone. The presence of Fe3+ (1.00·10−4M) enhanced Am3+ sorption at pcH∼4 but suppressed it from pcH of 5 to 9; 1.00·10−4M of Ca2+ and of UO2 2+ ions had no effect on the sorption profile.

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Abstract  

Sorption and desorption of radioeuropium on red earth and its solid components to remove organic matter was studied at pH 5.3±0.1 and 4.5±0.1, and in 0.01M and 0.001M NaClO4 solutions, respectively. Eu(III) sorption showed strong pH and humic acid concentration dependency, and NaClO4 concentration independency. The sorption increased with increasing pH and amount of HA adsorbed on red earth. The sorption of Eu(III) on red earth was mainly dominated by surface complexation. Humic acid and high pH had a great tendency to immobilize the movement of Eu(III) in red earth. Sorption-desorption hysteresis of Eu(III) on red earth indicated that the sorption was irreversible.

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Abstract  

Humic acids (HAs) extracted from soils developed under two Norwegian spruce (Picea abies, (L.) Karst) subalpine forests of northern Italy were characterized using chemical, thermal (TG-DTA) and spectroscopic (DRIFT) analyses. The samples were taken from five sites which differed in orientation (northern and southern exposure) and vegetal cover at different old age: grassland, regeneration, immature and mature stands. In general, the thermal patterns of HAs were similar (three exothermic reactions appeared around at 300, 400 and 500C) in both sites in grasslands and regeneration while a considerable modification appeared in HA from stands of different age at northern and southern exposure site. DRIFT spectroscopy confirmed the differences observed through TG-DTA analysis. In particular the main structural changes were ascribed to modification of carbonyl group and of CH stretching in aliphatic components in each HAs from different sites.

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Application of salt stress (100 mM) through root growing medium caused a considerable decrease in plant fresh and dry biomass, maximum quantum yield (F v/F m), chlorophyll contents, leaf water potential, and leaf Ca, K, P and N concentrations of two maize cultivars (Apex 836 and DK 5783). However, salt-induced increase was observed in leaf osmolality (LO), proline, hydrogen peroxide (H2O2), malondialdehyde (MDA), Na+ concentration and activities of enzymatic antioxidants, such as catalase (CAT), peroxidase (POD) and superoxide dismutase (SOD). Of five humic acid (HA) levels used under non-stress and stress conditions in an initial experiment, 100 mg L−1 was chosen for subsequent studies. Exogenous application of humic acid (HA) at the rate of 100 mM as a foliar or pre-sowing seed treatment significantly increased the plant biomass, F v/F m, chlorophyll pigments and proline contents, while it considerably reduced the leaf water potential, H2O2 and MDA contents as well as the activities of all the afore-mentioned enzymatic antioxidants. Of both modes of exogenous treatment, foliar spray was better in improving plant biomass, chlorophyll contents, LO, leaf Na+ as well as the accumulation of all nutrients measured, however, in contrast, seed pre-treatment was more effective in altering leaf proline, H2O2 and MDA contents. Of both maize cultivars, cv. DK 5783 excelled in plant biomass, chlorophyll contents and leaf N, Ca and K concentrations as well as in the activities of all three antioxidant enzymes, whereas cv. Apex 836 was superior in leaf Na+ and P concentrations, H2O2 and MDA contents. Cv. DK 5783 was comparatively better in salt tolerance as compared to cv. Apex 836. Overall, exogenous application of HA was effective in improving salinity tolerance of maize plants which can be attributed to HA-induced increase in plant biomass, chlorophyll contents, mineral nutrients and activities of key antioxidant enzymes.

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