Effect of pH,ionic strength,fulvic acid and humic acid on sorption of Th(IV) on Na-rectorite

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.     

Sorption of Th(IV) on MX-80 bentonite: effect of pH and modeling

MX-80 bentonite was characterized by XRD and FTIR in detail. The sorption of Th(IV) on MX-80 bentonite was studied as a function of pH and ionic strength in the presence and absence of humic acid/fulvic acid. The results indicate that the sorption of Th(IV) on MX-80 bentonite increases from 0 to 95% at pH range of 0–4, and then maintains high level with increasing pH values. The sorption of Th(IV) on bentonite decreases with increasing ionic strength. The diffusion layer model (DLM) is applied to simulate the sorption of Th(IV) with the aid of FITEQL 3.1 mode. The species of Th(IV) adsorbed on bare MX-80 bentonite are consisted of “strong” species o \textYOHTh^{4 +} \equiv {\text{YOHTh}}^{4 + } at low pH and “weak” species o \textXOTh(OH)₃ \equiv {\text{XOTh(OH)}}_{3} at pH > 4. On HA bound MX-80 bentonite, the species of Th(IV) adsorbed on HA-bentonite hybrids are mainly consisted of o \textYOThL₃ \equiv {\text{YOThL}}_{3} and o \textXOThL₁ \equiv {\text{XOThL}}_{1} at pH < 4, and o \textXOTh(OH)₃ \equiv {\text{XOTh(OH)}}_{3} at pH > 4. Similar species of Th(IV) adsorbed on FA bound MX-80 bentonite are observed as on FA bound MX-80 bentonite. The sorption isotherm is simulated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models, respectively. The sorption mechanism of Th(IV) on MX-80 bentonite is discussed in detail.     

Sorption of Th(IV) on goethite: effects of pH,ionic strength,FA and phosphate

Sorption of thorium (IV) on goethite was investigated as a function of contact time, pH, ionic strength, anions, solid-to-liquid ratio (m/V) and Th(IV) concentration using batch technique. The results showed that the sorption of Th(IV) was strong pH-dependence, and increased from ~10 to ~100% over the pH range of 2.0–4.0, and then kept a constant level in the higher pH range. The sorption of Th(IV) increased with increasing m/V and independent of ionic strength. It was clear that phosphate and FA significantly enhanced Th(IV) sorption on goethite. The sorption and desorption isotherms were investigated at pH 2.90 ± 0.05 and analyzed with Freundlich and Langmuir models, respectively. Compared to Langmuir model, Freundlich model could fit the experimental data better, according to the high relative coefficients.     

Investigation of radionuclide <Superscript>63</Superscript>Ni(II) sorption on ZSM-5 zeolite

The sorption of ⁶³Ni(II) from aqueous solution using ZSM-5 zeolite was investigated by batch technique under ambient conditions. ZSM-5 zeolite was characterized by point of zero net proton charge (PZNPC) titration. The sorption was investigated as a function of shaking time, pH, ionic strength, foreign ions, humic acid (HA), fulvic acid (FA) and temperature. The results indicate that the sorption of ⁶³Ni(II) on ZSM-5 zeolite is strongly dependent on pH. The sorption is dependent on ionic strength at low pH, but independent of ionic strength at high pH values. The presence of HA/FA enhances ⁶³Ni(II) sorption at low pH values, whereas reduces ⁶³Ni(II) sorption at high pH values. The sorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters (i.e., ∆H ⁰, ∆S ⁰ and ∆G ⁰) for the sorption of ⁶³Ni(II) are determined from the temperature dependent sorption isotherms at 293.15, 313.15 and 333.15 K, respectively, and the results indicate that the sorption process of ⁶³Ni(II) on ZSM-5 zeolite is spontaneous and endothermic.     

Modifying attapulgite clay by ammonium citrate tribasic for the removal of radionuclide Th(IV) from aqueous solution

The ammonium citrate tribasic was successfully modified to attapulgite clay and the effect of modifying was characterized by FTIR and XRD techniques. Experimental results showed that the ammonium citrate tribasic modified attapulgite clay had a strong sorption ability to remove Th(IV) from aqueous solutions. The sorption of Th(IV) from aqueous solutions has been systematically investigated as a function of several variables including contact time, solid content, pH, ionic strength, Fulvic acid (FA)/humic acid (HA) and temperature under ambient conditions. The results indicate that the sorption of Th(IV) onto ammonium citrate tribasic modified attapulgite clay is strongly dependent on pH, Th(IV) initial concentration, ionic strength, temperature and HA/FA. Surface complexation and ionic exchange are the main sorption mechanisms. Sorption of Th(IV) onto ammonium citrate tribasic modified attapulgite is quick and can be fitted by a pseudo-second-order rate model very well. Sorption of Th(IV) onto ammonium citrate tribasic modified attapulgite is promoted at higher temperature and the sorption reaction is an endothermic process. Langmuir isotherm model fits the experimental data better than Freundlich and D-R isotherm models. The results suggest that the ammonium citrate tribasic modified attapulgite sample is a suitable material in the preconcentration and solidification of radionuclide Th(IV) from large volumes of aqueous solutions.     

Meet the Cerium(IV) Phosphate Sisters: CeIV(OH)PO4 and CeIV2O(PO4)2

Two new cerium(IV) phosphates were obtained: cerium(IV) hydroxidophosphate, Ce(OH)PO₄, and cerium(IV) oxidophosphate, Ce₂O(PO₄)₂, which were shown to complement the classes of isostructural compounds M(OH)PO₄ and R₂O(PO₄)₂, where M=Th, U and R=Th, U, Np, Zr. Ce₂O(PO₄)₂ oxidophosphate is formed by elimination of H₂O from the crystal structure of Ce(OH)PO₄ during its thermal decomposition. The structures of Ce(OH)PO₄ and Ce₂O(PO₄)₂ are related to each other with the same Cmce space group and similar unit cell parameters (a=6.9691(3) Å, b=9.0655(4) Å, c=12.2214(4) Å, V=772.13(8) ų, Z=8; a=7.0220(4) Å, b=8.9894(5) Å, c=12.544(1) Å, V=791.8(1) ų, Z=4, respectively).     

Sorption of thorium(IV) from aqueous solutions by graphene oxide

Graphene oxide (GO) is one of the most important carbon nano-materials. In this paper, GO was synthesized from flake graphite and characterized by transmission electron microscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. The sorption of Th(IV) on GO was investigated as a function of contact time, solid-to-liquid ratio, pH, ionic strength, and in the presence of fulvic acid (FA) and humic acid (HA) by batch experiments. The sorption percentage of Th(IV) on GO decreased with increasing ionic strength and decreasing solid-to-liquid ratio. The sorption edge of Th(IV) in the presence of FA/HA is much lower than that in the absence of FA/HA. Furthermore, the sorption processes of Th(IV) can be described by a pseudo-second order rate model. Based on the Langmuir model, the maximum sorption capacities (Cs_max) of Th(IV) were about 5.80 × 10^?4 mol/L. From thermodynamic investigation, sorption of Th(IV) on GO is spontaneous and endothermic in nature. The rapid sorption rate and high sorption capacity suggest that GO is a promising adsorbent for Th(IV).     

Sorption behavior of germanium(IV) on titanium dioxide nanoparticles

Titanium dioxide nanoparticles were employed for the sorption of Ge(IV) ions from aqueous solution. The process was studied in detail by varying the sorption time, pH, and temperature. The sorption process was found to be fast, equilibrium was reached within 3 min. A maximum sorption could be achieved from solution when the pH ranges between 4.0 and 11.0. Sorbed Ge(IV) ions can be completely desorbed with 2 mL of 0.3 mol L⁻¹ K₃PO₄-1.0 mol L⁻¹ H₂SO₄ mixture solution. The kinetic experimental data properly correlate with the second-order kinetic model (k ₂ = 0.88 g mg⁻¹ min⁻¹ (25°C)), Reichenberg equation and Morris-Weber model. The estimated E _a for Ge(IV) adsorption on nano-TiO₂ was 19.66 kJ mol⁻¹. The overall rate process appears to be influenced by intra-particle diffusion. The sorption data could be well interpreted with the Langmuir and Dubinin-Radushkevich (D-R) type sorption isotherms. The D-R parameters were calculated to be K = −0.00321 mol₂ kJ⁻², q _m = 0.59 mmol g⁻¹ and E = 12.48 kJ mol⁻¹ at room temperature. Furthermore, the thermodynamic parameters were also determined, and the ΔH ⁰ and ΔG ⁰ values indicated a spontaneous exothermic behavior.     

Sorption properties of oxides IX: Effect of anions on the sorption of uranium (VI) on hydrous oxides

Effect of anions such as nitrate, chloride, sulphate and carbonate on the sorption of U(VI), from aqueous solutions on hydrous oxides of Ti(IV), Ce(IV) Zr(IV) and Th(IV) has been studied. The sorption of U(VI) is markedly reduced in the presence of anions, like carbonate, whichform strong complexes with UO ₂ ^{2 +} in solution. The results are explained in terms of a competition for free UO ₂ ^{2 +} between surface hydroxyl groups and ligands (anions) present in solution. The sorption of U(VI) on these hydrous oxides was also studied from a bicarbonatecarbonate mixture. Sorption was less under conditions when tricarbonate complex of U(VI) was formed, but increased at higher pH values (>9), presumably due to the formation and sorption of hydroxo complexes of U(VI).     

Phase formation in the ZrO(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-H<Subscript>3</Subscript>PO<Subscript>4</Subscript>-CsF-H<Subscript>2</Subscript>O system at low concentration of the phosphorus-containing component

The ZrO(NO₃)₂-H₃PO₄-CsF-H₂O system was studied at 20°C along the section at a molar ratio of PO₄³⁻/Zr = 0.5 (which is of the greatest interest in the context of phase formation) at ZrO₂ concentrations in the initial solutions of 2–14 wt % and molar ratios of CsF: Zr = 1−6. The following compounds were isolated for the first time: crystalline fluorophosphates CsZrF₂PO₄ · H₂O, amorphous oxofluorophosphate Cs₂Zr₃O₂F₄(PO₄)₂ · 3H₂O, and amorphous oxofluorophosphate nitrate CsZr₃O_1.25F₄(PO₄)₂(NO₃)_0.5 · 4.5H₂O. The compound Cs₃Zr₃O_1.5F₆(PO₄)₂ · 3H₂O was also isolated, which forms in a crystalline or glassy form, depending on conditions. The formation of the following new compounds was established: Cs₂Zr₃O_1.5F₅(PO₄)₂ · 2H₂O, Cs₂Zr₃F₂(PO₄)₄ · 4.5H₂O, and Zr₃O₄(PO₄)_1.33 · 6H₂O, which crystallize only in a mixture with known phases. All the compounds were studied by X-ray powder diffraction, crystal-optical, thermal, and IR spectroscopic analyses.     

Impact of environmental conditions on the sorption behavior of Co(II) on Na-rectorite studied by batch experiments

The sorption of Co(II) from aqueous solution on Na-rectorite was investigated under ambient conditions. Experiments were carried out as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid and temperature. The results indicated that the sorption of Co(II) was strongly dependent on pH. At low pH the sorption was dominated by outer-sphere surface complexation or ion exchange, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms at three different temperatures. The thermodynamic data (∆G ⁰, ∆S ⁰, ∆H ⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Co(II) on Na-rectorite was spontaneous and endothermic. Experimental results indicate that Na-rectorite is a suitable adsorbent for preconcentration and solidification of Co(II) from large volumes of aqueous solutions.     

Sorption of radioeuropium onto attapulgite: effect of experimental conditions

Batch sorption experiments were performed to remove Eu(III) ions from aqueous solutions by using attapulgite under ambient conditions. Different experimental conditions, such as contact time, solid content, foreign ions, pH, ionic strength, fulvic acid and temperature, have been investigated to study their effect on the sorption property. The results indicated that the sorption of Eu(III) onto attapulgite was strongly dependent on pH, ionic strength and temperature. The sorption increased from about 8.9 to 90% at pH ranging from 2 to 6 in 0.01 mol/L NaNO₃ solution. The Eu(III) kinetic sorption on attapulgite was fitted by the pseudo-second-order model better than by the pseudo-first-order model. The sorption of Eu(III) onto attapulgite increased with increasing temperature and decreasing ionic strength. The Langmuir and Freundlich models were used to simulate the sorption isotherms, and the results indicated that the Freundlich model simulated the data better than the Langmuir model. The thermodynamic parameters (∆G ^o, ∆S ^o, ∆H ^o) were determined from the temperature dependent isotherms at 298.15, 318.15 and 338.15 K, and the results indicated that the sorption reaction was an endothermic and spontaneous process. The results suggest that the attapulgite is a suitable material as an adsorbent for preconcentration and immobilization of Eu(III) from aqueous solutions.     

Sorption of cesium from water solutions on potassium nickel hexacyanoferrate-modified <Emphasis Type="Italic">Agaricus bisporus</Emphasis> mushroom biomass

In order to gain biosorbent that would have the ability to bind cesium ions from water solution effectively, potassium nickel hexacyanoferrate(II) (KNiFC) was incorporated into the mushroom biomass of Agaricus bisporus. Cesium sorption by KNIFC-modified A. bisporus biosorbent was observed in batch system, using radiotracer technique using ¹³⁷Cs radioisotope. Kinetic study showed that the cesium sorption was quite rapid and sorption equilibrium was attained within 1 h. Sorption kinetics of cesium was well described by pseudo-second order kinetics. Sorption equilibrium was the best described by Freundlich isotherm and the distribution coefficient was at interval 7,662–159 cm³ g⁻¹. Cesium sorption depended on initial pH of solution. Cesium sorption was very low at pH₀ 1.0–3.0. At initial pH 11.0, maximum sorption of cesium was found. Negative effect of monovalent (K⁺, Na⁺, NH₄ ⁺) and divalent (Ca²⁺, Mg²⁺) cations on cesium sorption was observed. Desorption experiments showed that 0.1 M potassium chloride is the most suitable desorption agent but the complete desorption of cesium ions from KNiFC-modifed biosorbent was not achieved.     

Sorption of radiocobalt(II) from aqueous solutions to Na-attapulgite

The sorption of Co(II) on Na-attapulgite as a function of contact time, solid content, pH, ionic strength, foreign ions, fulvic acid (FA) and temperature under ambient conditions was studied. The kinetic of Co(II) sorption on Na-attapulgite was described well by pseudo-second-order model. The sorption of Co(II) on Na-attapulgite was strongly dependent on pH and ionic strength. The sorption of Co(II) was mainly dominated by outer-sphere surface complexation and/or ion exchange at low pH, whereas inner-sphere surface complexation or surface precipitation was the main sorption mechanism at high pH values. The presence of FA did not affect Co(II) sorption obviously at pH <7, and a negative effect was observed at pH >7. The Langmuir and Freundlich models were used to simulate the sorption data at different temperatures, and the results indicated that the Langmuir model simulated the data better than the Freundlich isotherm model. The thermodynamic parameters (∆G°, ∆S°, ∆H°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on Na-attapulgite was an endothermic and spontaneous process. The results suggest that the attapulgite sample is a suitable material in the preconcentration and solidification of radiocobalt from large volumes of aqueous solutions.     

Effect of pH,ionic strength,foreign ions,humic acid and temperature on sorption of radionuclide <Superscript>60</Superscript>Co(II) on illite

In this article, a series of batch experiments were carried out to investigate the effect of various environmental factors such as contact time, solid content, pH, ionic strength, foreign ions, temperature and coexisting humic acid on the sorption behavior radionuclide ⁶⁰Co(II) on illite. The results indicated that the sorption of Co(II) was strongly dependent on pH, ionic strength and temperature. At low pH, the sorption was dominated by outer-sphere surface complexation and ion exchange on illite surfaces, whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were used to simulate the sorption isotherms at three different temperatures of 303.15, 323.15 and 343.15 K. The thermodynamic data (∆G ⁰, ∆S ⁰, ∆H ⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Co(II) on illite was an endothermic and spontaneous process. The sorption test revealed that the illite can be as a cost-effective adsorbent suitable for pre-concentration of Co(II) from large volumes of aqueous solutions.     

Phase formation in the ZrO(NO3)2-H3PO4-RbF-H2O system: the PO 43? /Zr = 0.5 section

We studied phase formation in the ZrO(NO₃)₂-H₃PO₄-RbF-H₂O system along PO₄³⁻/Zr = 0.5 (mol/mol) and RbF/Zr = 1–5 (mol/mol) sections with 2–10 wt % ZrO₂ in the starting solution. We recovered amorphous rubidium oxofluorophosphatozirconate Rb₂Zr₃OF₆(PO₄)₂ · 2H₂O and the following fluorophosphatonitratozirconates: Rb₂ZrF₄(PO₄)_0.33NO₃, which forms large cubic system crystals; weakly crystallized RbZr₃OF₃(PO₄)₂(NO₃)₂ · 5H₂O; and amorphous Zr₃OF₃(PO₄)₂NO₃ · (7–8) H₂O. A shown by its IR spectrum, Rb₂ZrF₄(PO₄)_0.33NO₃ contains NO₃- and PO₄ groups that are not coordinated to zirconium, meaning that this is a triple salt ZrF₄ · Rb(PO₄)_0.33 · RbNO₃. The formula units of the RbZr₃OF₃(PO₄)₂(NO₃)₂ · 5H₂O and Zr₃OF₃(PO₄)₂NO₃ · (7–8)H₂O phases are only conventional. All compounds have been recovered for the first time.     

Infrared spectroscopy and the structure of La0.33Zr2(Po4)3-Yb0.33Zr2(PO4)3 solid solutions

Solid solutions of double orthophosphates of zirconium and rare earth lanthanum and ytterbium (La_0.33Zr₂(PO₄)₃-Yb_0.33Zr₂(PO₄)₃) that belong to the NASICON (NZP) structural type are synthesized and studied by IR spectroscopy. The factor-group analysis of P-O vibrations in phosphates with P3 (La_0.33Zr₂(PO₄)3) and P3c (Yb_0.33Zr₂(PO₄)₃) space groups allows us to assign the intermediate representatives of this series to two different space groups by their IR spectra, which is difficult to perform based on powder X-ray diffraction results. A morphotropic transition P3 → P3 c is found to occur near the La_1/18Yb_5/18Zr₂(PO₄)₃ composition.     

Sorption of U(VI) onto a decarbonated calcareous soil

Sorption of U(VI) from aqueous solution to decarbonated calcareous soil (DCS) was studied under ambient conditions using batch technique. Soil samples were characterized by XRD, FT-IR and SEM in detail and the effects of pH, solid-to-liquid ratio (m/V), temperature, contact time, fulvic acid (FA), CO₂ and carbonates on U(VI) sorption to calcareous soil were also studied in detail using batch technique. The results from experimental techniques showed that sorption of U(VI) on DCS was significantly influenced by pH values of the aqueous phase, indicating a formation of inner-sphere complexes at solid–liquid interface, and increased with increasing temperature, suggesting the sorption process was endothermic and spontaneous. Compared to Freundlich model, sorption of U(VI) to DCS was simulated better with Langmuir model. The sorption equilibrium could be quickly achieved within 5 h, and sorption results fitted pseudo-second-order model well. The presence of FA in sorption system enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH values. In absence of FA, the sorption of U(VI) onto DCS was an irreversible process, while the presence of FA reinforced the U(VI) desorption process reversible. The presence of CO₂ decreased U(VI) sorption largely at pH >8, which might due to a weakly adsorbable formation of Ca₂UO₂(CO₃)₃ complex in aqueous phase.     

Synthesis and characterization of O,O′-dialkyl and alkylene dithiophosphates of thorium(IV) and their adducts with nitrogen and phosphorus donors

Thorium(IV) tetrakis(dithiophosphates), [Th{S₂P(OR)₂}₄] (where R?=?–CH₂CH₂CH₃ or –C₆H₅) and [Th{S₂PO₂G}₄] [where G?=?–C(CH₃)₂CH₂CH(CH₃)–, –CH₂C(CH₃)₂CH₂–, –C(CH₃)₂C(CH₃)₂– and –CH₂CH₂CH(CH₃)–] were prepared in methanolic solution of Th(NO₃)₄???6H₂O and ammonium dithiophosphates. Adducts of the type [Th{S₂P(OR)₂}₄???nL] and [Th{S₂PO₂G}₄???nL] [where n?=?1, L?=?N₂C₁₀H₈ or N₂C₁₂H₈ and n?=?2, L?=?P(C₆H₅)₃] were prepared by the reaction of thorium(IV) tetrakis(dithiophosphates) and nitrogen or phosphorus donors in benzene. These newly synthesised derivatives have been characterized by elemental analyses, molecular weights, IR, ¹H and ³¹P NMR spectral measurements. Coordination numbers of eight and ten are suggested for thorium(IV) in these derivatives.     

Preparation of Zr(IV)/Nb(V) Nasicon-like phosphates by a sol-gel method

The NbZr(PO₄)₃ and Na_0.5Nb_0.5Zr_1.5(PO₄)₃ Nasicon-like phases were prepared by the sol-gel method using (NH₄)₃ [NbO(C₂O₄)₃]·1.5H₂O, ZrOCl₂·8H₂O and NH₄H₂PO₄ in oxalic or tartaric acid mediums. The thermal evolution of the xerogels prepared was followed by XRD and IR techniques. Depending on reaction conditions, such as, pH and Zr⁴⁺/organic acid ratio, pure Nasicon-like phases can be prepared at different temperatures.