Sorption of Th (IV) to silica as a function of pH, humic/fulvic acid, ionic strength, electrolyte type.

The removal behavior of thorium (Th(IV)) has been investigated in multicomponent systems containing silica (SiO2) as the model of inorganic particles because of its widespread presence in the earth's crust and soil humic acid (HA)/fulvic acid (FA) by batch experiments. The influence of pH from 2 to 12, ionic strength from 0.02 to 0.2 M KNO3, soil HA/FA concentration from 8.3 to 22.5 mg/L, and foreign cations (Li+, Na+, K+) and anions (NO3(-), Cl-) on the sorption of Th(IV) onto SiO2 was also tested. The sorption isotherms of Th(IV) at approximately constant pH (3.50+/-0.02) were determined and analyzed regressively with three kinds of sorption isotherm models, i.e., linear, Langmuir, and Freundlich models. The results demonstrated that the sorption of Th(IV) onto SiO2 increased steeply with increasing pH from 2 to 4. Generally, humic substances (HSs) were shown to enhance Th(IV) sorption at low pH, but to reduce Th(IV) sorption at intermediate and high pH. It was a hypothesis that the significantly positive influence of HA/FA at pH from 2 to 4 on the sorption of Th(IV) onto SiO2 was attributed to strong surface binding of HA/FA on SiO2 and subsequently the formation of ternary surface complexes such as [triple bond]MO-O-HA-Th or [triple bond]MO-O-FA-Th. The results also demonstrated that the sorption was strongly dependent on the concentration of HA/FA, and independent of ionic strength and foreign ions under our experimental conditions.     

Effect of pH, ionic strength and fulvic acid on the sorption and desorption of cobalt to bentonite.

Humic substances and bentonite have attracted great interest in radioactive waste management. Here the sorption of cobalt on bentonite in the presence and absence of fulvic acid (FA) under ambient conditions was studied. The effects of pH, ionic strength, FA and solution concentrations on cobalt sorption to bentonite were also investigated using batch techniques. The results indicate that the sorption of cobalt is strongly dependent on pH and is independent of ionic strength under our experimental conditions. Surface complexation is considered the main mechanism of cobalt sorption to bentonite. In the presence of FA, little effect of FA on cobalt sorption was found at pH<6; a positive effect of FA on cobalt sorption was found for pH 6-8; and a negative effect of FA on cobalt sorption was found at pH>8. The addition sequences of FA/Co(2+) to the bentonite suspension on the sorption of cobalt to FA-coated bentonite were also studied. The results indicated that the sorption is not influenced by the addition sequences. Some possible mechanisms are discussed.     

Sorption-desorption of Th(IV) on attapulgite: effects of pH, ionic strength and temperature.

The sorption of Th(IV) on attapulgite was studied as a function of pH, ionic strength, temperature, attapulgite contents and Th(IV) concentrations under ambient conditions using a batch technique. The results indicated that sorption of Th(IV) on attapulgite was strongly affected by pH values, and weakly dependent on ionic strength. Sorption of Th(IV) was dominated by surface complexation, although ion exchange also contributed to this sorption. Sorption of Th(IV) increased with increasing temperature of the system. Enthalpy (DeltaH(0)), entropy (DeltaS(0)) and Gibbs free energy (DeltaG(0)) were calculated from the temperature-dependent sorption data; the results indicated that the sorption of Th(IV) on attapulgite was a spontaneous process. Sorption-desorption hysteresis indicated that the sorption of Th(IV) was irreversible, and that the Th(VI) adsorbed on attapulgite was difficult to be desorbed from solid to liquid phases.     

Thermodynamic study of Th(IV) sorption on attapulgite

Sorption of Th(IV) on attapulgite was studied as a function of pH and temperature under ambient conditions using batch technique. The results indicated that sorption of Th(IV) on attapulgite was strongly affected by pH values and temperature. The kinetic sorption of Th(IV) can be described by pseudo-second-order rate very well. Sorption isotherms of Th(IV) at 293.15, 308.15 and 323.15 K were modeled by Langmuir and Dubinin–Radushkevich models very well, and the parameters indicated that the sorption of Th(IV) on attapulgite was strongly dependent on temperature and the sorption of Th(IV) increased with increasing temperature of the system. Enthalpy (ΔH⁰), entropy (ΔS⁰) and Gibbs free energy (ΔG⁰) were calculated from the temperature dependent sorption data, and the results indicated that the sorption of Th(IV) on attapulgite was a spontaneous process, and the sorption was endothermic.     

Sorption properties of Th(IV) on the raw diatomite-Effects of contact time, pH, ionic strength and temperature.

Diatomite has a number of unique physicochemical properties and has diversified industrial uses. Natural diatomite has been tested as a potential sorbent for the removal of Th(IV) from aqueous solutions. The results indicate that sorption of Th(IV) is strongly dependent on ionic strength at pH<3, and is independent of ionic strength at pH>3. Outer-sphere complexation or ion exchange may be the main sorption mechanism of Th(IV) to diatomite at low pH values, whereas the sorption of Th(IV) at pH>3 is mainly dominated by inner-sphere complexation or precipitation. The competition for Th(IV) between aqueous or surface adsorbed anions (e.g., herein ClO(4)(-), NO(3)(-) and Cl(-)) and surface functional groups of diatomite is important for Th(IV) sorption. The thermodynamic data (DeltaH(0), DeltaS(0), DeltaG(0)) are calculated from the temperature-dependent sorption isotherms. The results suggest that sorption process of Th(IV) on diatomite is spontaneous and endothermic.     

Sorption and complexation of Eu(III) on alumina: effects of pH, ionic strength, humic acid and chelating resin on kinetic dissociation study.

The effects of pH (pH=2-12), ionic strength (0.01-2 mol/l NaNO(3)) and humic acid on the sorption and complexation of Eu(III) on alumina were investigated by using batch techniques. The experiments were carried out at room temperature and under ambient conditions. The results indicate that the sorption of Eu(III) on alumina is strongly influenced by humic acid. The sorption of Eu(III) on alumina is significantly dependent on pH values and independent of ionic strength. The sorption of Eu(III) on alumina may be attributed to surface complexation. The species of Eu(III) on HA-alumina colloids is dominated by both HA and alumina, and the addition sequences of HA or Eu(III) to the ternary system do not influence the sorption of Eu(III) to HA-coated alumina. Kinetic dissociation of Eu(III) from bare and HA-coated alumina was also studied by using the chelating resin. The result was discussed by a pseudo-first-order kinetics model.     

Sorption and desorption of Eu and Yb on alumina: mechanisms and effect of fulvic acid.

The effects of pH, ionic strength and FA (fulvic acid) on the sorption and desorption of Eu(III) and Yb(III) on alumina were respectively investigated by using batch technique and radiotracers 152 + 154Eu and 169Yb. The distribution coefficients for sorption and desorption of Eu on alumina at pH 4.4, 4.6 and 5.7 in 1 mol/l NaCl solutions as a function of solid phase concentration were determined in the presence or absence of FA. The effects of pH, FA and ionic strength on the distribution coefficients for sorption and desorption of Yb on alumina were determined in 0.01-2.0 mol/l NaNO3. It was found that pH and FA influenced the sorption of Eu(III) and Yb(III) on alumina greatly. A surface hydrolysis model can satisfactorily and qualitatively explain the observations on bare alumina. The competition among the complexations of surface free hydroxyl groups, soluble and sorbed fulvic acids can satisfactorily and qualitatively explain the observations on the coated alumina.     

Sorption of Ni(II) on GMZ bentonite: Effects of pH, ionic strength, foreign ions, humic acid and temperature

Bentonite has been widely studied in nuclear waste management because of its special physicochemical properties. In this work, the sorption of Ni(II) from aqueous solution onto GMZ bentonite as a function of contact time, pH, ionic strength, foreign ions, humic acid (HA) and temperature was investigated under ambient conditions. The results indicated that the pseudo-second-order rate equation simulated the kinetic sorption process well. The sorption of Ni(II) on GMZ bentonite was strongly dependent on pH and on ionic strength. At low pH, the sorption of Ni(II) was dominated by outer-sphere surface complexation and ion exchange with Na⁺/H⁺ on GMZ bentonite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. A positive effect of HA on Ni(II) sorption was found at pH<8, whereas a negative effect was observed at pH>8. The Langmuir, Freundlich, and D-R models were used to simulate the sorption isotherms of Ni(II) at three different temperatures: 303.15, 318.15 and 333.15 K. The thermodynamic parameters (ΔH⁰, ΔS⁰ and ΔG⁰) of Ni(II) sorption on GMZ bentonite at the three different temperatures were calculated from the temperature-dependent sorption isotherms. The results indicated that the sorption process of Ni(II) on GMZ bentonite was endothermic and spontaneous. Experimental results indicate that GMZ bentonite is a suitable sorbent for pre-concentration and solidification of Ni(II) from large volume solutions.     

Sorption and desorption of radiocobalt on montmorillonite--effects of pH, ionic strength and fulvic acid.

Humic substances and clay minerals have been studied extensively in radioactive waste management. In our research, the sorption and desorption of radiocobalt on montmorillonite in the presence and absence of fulvic acid as a function of pH and ionic strength were investigated under ambient conditions by using batch techniques. The results indicate that the sorption of cobalt is strongly dependent on pH values and independent of ionic strength. Surface complexation rather than cation exchange is considered as the main mechanism of cobalt sorption to montmorillonite. The presence of fulvic acid enhances cobalt sorption obviously at pH values<8. The desorption behavior changes of surface-sorbed cobalt from montmorillonite were studied by decreasing pH values and the solution cobalt concentrations independently. The results indicated that the sorption of cobalt on montmorillonite is irreversible.     

175Yb-labeled hydroxyapatite: a potential agent for use in radiation synovectomy of small joints

The preparation of 175Yb-labeled hydroxyapatite (HA) particle is described for possible use as an agent for radiation synovectomy (RS) of small-sized joints. 175Yb was produced by thermal neutron irradiation of enriched (98.6% in 174Yb) ytterbium target at a flux of approximately 3 x 10(13) n/cm(2)/s for 7 days. Specific activity of 5.5-6.0 GBq/mg and a very high radionuclidic purity to the extent of approximately 100% were obtained. In the work reported herein, HA could be labeled with 175Yb in very high radiochemical purity (>99%) using 10 mg of HA particle at pH approximately 7. The radiolabeled particulates showed excellent in vitro stability at room temperature. Serial scintigraphic images of normal as well as arthritis-bearing Wistar rats following intra-articular injection of 175Yb-HA particles in the knee joint showed complete retention of activity within the synovial cavity with no measurable activity leaching out from the joint till 144 h post-injection.     

Comparative study on sorption/desorption of radioeuropium on alumina, bentonite and red earth: effects of pH, ionic strength, fulvic acid, and iron oxides in red earth.

The sorption and desorption of Eu(III) as a representative of trivalent lanthanides and actinides on bentonite, alumina, red earth and red earth treated to remove free iron oxides were comparatively investigated by using batch technique and radiotracer 152 + 154Eu. The effects of pH, ionic strength, fulvic acid, iron oxides in red earth and the sorption mechanism were also discussed. As compared to alumina and red earth, Eu(III) presents a considerable distribution coefficient (Kd) onto bentonite. It was found that the pH and the presence of clay minerals are the main factors dominating the sorption/desorption characteristic of Eu3+ in the soil, and that a sorption-desorption hysteresis on bentonite and red earth actually occurs. Furthermore, the main sorption mechanism of lanthanides onto bentonite, alumina and red earth is the formation of bridged hydroxo complexes with the surface, and there are negative effects of fulvic acid and free iron oxides in red earth on the sorption of Eu(III). The results of this paper indicate that the additivity rule on the sorption characteristic of a soil from the individual component's characteristics is not general.     

Modulation of immune response by the acute and chronic exposure to high altitude

PURPOSE: The chronic exposure at high altitude (HA) represents an ideal model for evaluating the in vivo effects of hypobaric hypoxia. Taking advantage of the EV-K2-CNR Pyramid, this study was designed to evaluate whether acute and chronic hypoxia differently modulates the in vivo immune responses. METHODS: The study includes 13 healthy female moderately active volunteers participating to the Italian HA project EV-K2-CNR. Peripheral blood lymphocytes, collected at sea level and at HA in the Pyramid Laboratory of CNR, Nepal (5050 m), were immunologically characterized by flow cytometry and a series of molecular and functional analyses. RESULTS: Flow cytometric analyses showed that: a) CD3+ T lymphocytes significantly decreased during both acute and chronic exposure to HA, b) T-cell fall was totally due to CD4+ T-cell reduction, c) B lymphocytes were not influenced by the exposure to HA, and d) natural killer (NK) cells significantly increased during acute and chronic exposure. The evaluation of the Th1/Th2 pattern demonstrated a significant decrease of the expression of the Th1 cytokine interferon-gamma (IFN-gamma) by circulating T cells during acute and chronic exposure to HA. The expression by T cells of CXCR3, a chemokine receptor typically expressed by Th1/Tc1 cells, paralleled the decrease of IFN-gamma. On the contrary, the expression of IL-4 was not conditioned by the exposure to HA. Finally, functional studies showed a significant reduction of the proliferative activity in response to mitogen (PHA) both in acute and chronic HA exposure. Despite the increased number of NK cells, NK cytotoxic activity was not influenced by the HA exposure. CONCLUSIONS: Our results indicate that the in vivo exposure to HA leads to an impairment of the homeostatic regulation of Th1/Th2 immune balance that potentially could favor long-term immunological alterations and increase the risk of infections.     

Effect of pH,ionic strength and temperature on the sorption of radionickel on Na-montmorillonite

Sorption of Ni(II) on Na-montmorillonite was studied under ambient conditions using the batch technique. The effects of pH, solid content, ionic strength and temperature on Ni(II) sorption was also investigated. The kinetic sorption process was well described by a pseudo-second-order rate model. The sorption thermodynamics of Ni(II) on montmorillonite were carried out at 20±2 °C, 37±2 °C, and 67±2 °C, respectively. The thermodynamic parameters, such as standard free energy changes (ΔG⁰), standard enthalpy change (ΔH⁰) and standard entropy change (ΔS⁰), were obtained. The sorption of Ni(II) is an endothermic process. The sorption of Ni(II) on montmorillonite was strongly dependent on pH values and temperature, and independent of ionic strength. At acidic pH, sorption of Ni(II) is dominated by cation exchange and outer-sphere surface complexation, but at alkaline pH the sorption is dominated by inner-sphere surface complexation.     

Sorption and desorption of Co(II) on alumina:: mechanisms and effect of humic substances

The effects of pH, ionic strength and humic substances on the sorption and desorption of Co(II) on alumina and silica were, respectively investigated by using radiotracer ⁶⁰Co. The distribution coefficients, the breakthrough curves and the displacement curves were experimentally determined in the batch and the column experiments. The pH and the humic substances influenced the sorption of Co(II) on alumina greatly as compared with the sorption of Co(II) on silica. It was found that the sorption characteristics of Co(II) onto alumina and silica are distinctly different, that the strong chemical bonds are formed between the bare alumina surface and Co(II) and between the coated alumina surface and Co(II), and that a transition from the adsorption to the surface-induced precipitation of Co(II) on the bare alumina surface takes place.     

188Re-labeled hydroxyapatite particles for radiation synovectomy.

A new procedure for labeling hydroxyapatite (HA) particles with 188Re for radiation synovectomy is described and standardized. The particles were labeled with 188Re in high yields (99%) in acidic medium. HA particle size remained unaffected by reaction conditions as checked by laser diffraction particle analyzer. 188Re-HA was found to be stable retaining 99% radiochemical purity after 4 days when stored in ascorbic acid solution (10mg/ml, pH 5). Intra-articular injection in rats revealed approximately 98% retention of 188Re-HA in the knee after 48-h pi.     

Scanning electron microscopy in the identification of fly artifacts

Bloodstain pattern analysis has a key role in crime scene reconstruction; however, it can be hampered by diverse confounding factors, such as insect activity which may lead to the production of small artifactual bloodstains, commonly referred to as fly artifacts (FA). Although several techniques aimed at distinguishing human bloodstains and FA have been developed, actually, no standardized and reproducible methodology is available. The aim of our study was to test the use of scanning electron microscopy (SEM) to distinguish human bloodstains from FA produced by Sarcophaga carnaria. FA and bloodstains have been produced on five different deposition surfaces under experimental conditions. After visual analysis, bloodstains and FA were analyzed at standard low (× 40–× 300) and high (× 600–× 1200) magnification through a Philips SEM 515. Although differential diagnosis between bloodstains and FA resulted often inconclusive at visual analysis, SEM analysis allowed the identification of additional key distinctive morphological features. In particular, on the surface of FA, small crystal-like and/or amorphous material deposits were observed. Such deposits were absent on bloodstains which, on the other hand, displayed red blood cells stacked in “rouleaux.” Basing on these results and under our experimental conditions, SEM analysis resulted suitable to perform a differential diagnosis between bloodstains and FA produced from the insect activity of Sarcophaga carnaria.

     

Sorption reaction mechanism of some hazardous radionuclides from mixed waste by impregnated crown ether onto polymeric resin

A novel impregnated polymeric resin was practically tested as adsorbent material for removal of some hazardous radionuclides from radioactive liquid waste. The applicability for the treatment of low-level liquid radioactive waste was investigated. The material was prepared by loading 4,4′(5′)di-t-butylbenzo 18 crown 6 (DtBB18C6) onto poly(acrylamide-acrylic acid-acrylonitril)-N, N′-methylenediacrylamide (P(AM-AA-AN)-DAM). The removal of ¹³⁴Cs, ⁶⁰Co, ⁶⁵Zn , and ^(152+154)Eu onto P(AM-AA-AN)-DAM/DtBB18C6 was investigated using a batch equilibrium technique with respect to the pH, contact time, and temperature. Kinetic models are used to determine the rate of sorption and to investigate the mechanism of sorption process. Five kinetics models, pseudo-first-order, pseudo-second-order, intra-particle diffusion, homogeneous particle diffusion (HPDM), and Elovich models, were used to investigate the sorption process. The obtained results of kinetic models predicted that, pseudo-second-order is applicable; the sorption is controlled by particle diffusion mechanism and the process is chemisorption. The obtained values of thermodynamics parameters, ΔH°, ΔS°, and ΔG° indicated that the endothermic nature, increased randomness at the solid/solution interface and the spontaneous nature of the sorption processes.     

Effect of pH, ionic strength and humic acid on the sorption of uranium(VI) to attapulgite

Attapulgite was investigated to remove UO₂²⁺ from aqueous solutions because of its strong sorption capacity. Herein, the attapulgite sample was characterized by Fourier transform infrared spectra (FTIR), X-ray diffraction (XRD) and acid–base titration in detail. Sorption of UO₂²⁺ on attapulgite was strongly dependent on pH values and ionic strength. The presence of humic acid enhanced the sorption of UO₂²⁺ on attapulgite obviously because of the strong complexation of humic acid (HA) with UO₂²⁺ on attapulgite surface. Sorption of UO₂²⁺ on attapulgite was mainly dominated by ion-exchange or outer-sphere complexation at low pH values, and by inner-sphere complexation at high pH values. The results indicated that attapulgite was a suitable material for the preconcentration and solidification of UO₂²⁺ from large volume of solutions because of its negative surface charge and large surface areas.     

Sorption and desorption of radiocesium on red earth and its solid components: relative contribution and hysteresis.

The relative contributions of organic matter and iron oxides to the Cs+ sorption on red earth were investigated by using the batch technique and selective extraction methods. The sorption and desorption isotherms and the distribution coefficients of Cs+ on the untreated red earth and the three treated soils to remove organic matter, iron oxides and organic matter plus iron oxides were determined at 20 degrees C, pH 6.3+/-0.2, in the presence of 0.01 mol/l CaCl2. It was found that all the isotherms are linear in the Cs+ concentration range used here, that the sorption desorption hysteresis on the red earth actually occurs, and besides the clay minerals, the organic matter present in the red earth is a significant trap of Cs+ and is responsible for the hysteresis instead of the iron oxides.     

Sorption characteristics of zinc(II) by calcareous soil-radiotracer study.

65Zn was used as a radiotracer to study the sorption characteristics of zinc by two calcareous soils from Gansu Province (China). The sorption and desorption isotherms of Zn on two untreated calcareous soils and on two soils treated to remove CaCO3 were determined at 20 +/- 2 degrees C, pH 7.8 +/- 0.2 in the presence of 0.001 mol/l CaCl2. The contribution of CaCO3 to the Zn sorption by the two calcareous soils was approximately 70% of the total amount sorbed and the sorption-desorption hysteresis was definitely demonstrated, thus the CaCO3 in calcareous soil is undoubtedly the most significant sink for zinc at high pH range.