Differential pulse polarographic determination of traces of iron in solar-grade silicon

Iron is determined, after volatilization of the matrix as hexafluorosilicic acid, by means of the polarographic iron(III) wave in a 0.1 M triethanolamine—0.1 M potassium bromate—0.5 M sodium hydroxide medium. Differential pulse polarography provides a detection limit of about 0.15 μg g^-1 with a precision of 1–2% and linear calibration graphs up to 0.5 μg Fe(III) ml^-1.     

Vacuum balance and related studies of green and red rusts

Green and red rusts are formed when iron is partially or completely oxidised. Analogues of the rusts may be precipitated from iron(II) and iron (III) salt solutions treated with alkali under reducing or oxidising conditions. Variations in surface area and porosity have been investigated by gravimetric nitrogen gas sorption, using vacuum microbalance techniques.Freshly-precipitated red rusts, hydrous iron (III) oxide, have surface areas of about 200–400 m²g^?1. When they are added to iron (II) hydroxide suspensions kept at pH 7, the green Fe (II)-Fe (III) rusts formed have lower surface areas of about 40–100 m²g^?1, depending on the initial iron(II) sulphate concentrations.     

Sorption of the long-lived radionuclides cesium-134, strontium-85 and cobalt-60 on bentonite

The sorption of long-lived radionuclides of cesium, strontium and cobalt (¹³⁴Cs, ⁸⁵Sr and ⁶⁰Co) on bentonite under various experimental conditions, such as contact time, pH, sorbent and sorbate concentrations have been studied. The uptake of Cs and Sr was rapid and equilibrium was reached almost instantaneously in both the cases, while Co sorption was time dependent. The sorption of these nuclides increased by increasing pH. The uptake of Cs, Sr and Co increased with increasing the amount of the bentonite clay. The percentage sorption for Cs, Sr and Co decreased with increasing metal concentrations. The desorption studies with 0.01M CaCl₂ and ground water at low-metal loadings on bentonite showed that about 95% of Cs, 85-90% of Sr and 97% of Co were irreversibly sorbed. These results could be helpful for nuclear waste management, for waste water effluents containing low concentrations of cesium, strontium and cobalt.     

Rapid determination of radiostrontium in seawater samples

A new method for the determination of radiostrontium in seawater samples has been developed at the Savannah River National Laboratory (SRNL) that allows rapid pre-concentration and separation of strontium and yttrium isotopes in seawater samples for measurement. The new SRNL method employs a novel and effective pre-concentration step that utilizes a blend of calcium phosphate with iron hydroxide to collect both strontium and yttrium rapidly from the seawater matrix with enhanced chemical yields. The pre-concentration steps, in combination with rapid Sr Resin and DGA Resin cartridge separation options using vacuum box technology, allow seawater samples up to 10 L to be analyzed. The total ⁸⁹Sr + ⁹⁰Sr activity may be determined by gas flow proportional counting and recounted after ingrowth of ⁹⁰Y to differentiate ⁸⁹Sr from ⁹⁰Sr. Gas flow proportional counting provides a lower method detection limit than liquid scintillation or Cerenkov counting and allows simultaneous counting of samples. Simultaneous counting allows for longer count times and lower method detection limits without handling very large aliquots of seawater. Seawater samples up to 6 L may be analyzed using Sr Resin for ⁸⁹Sr and ⁹⁰Sr with a minimum detectable activity (MDA) of 1–10 mBq/L, depending on count times. Seawater samples up to 10 L may be analyzed for ⁹⁰Sr using a DGA Resin method via collection and purification of ⁹⁰Y only. If ⁸⁹Sr and other fission products are present, then ⁹¹Y (beta energy 1.55 MeV, 58.5 day half-life) is also likely to be present. ⁹¹Y interferes with attempts to collect ⁹⁰Y directly from the seawater sample without initial purification of Sr isotopes first and ⁹⁰Y ingrowth. The DGA Resin option can be used to determine ⁹⁰Sr, and if ⁹¹Y is also present, an ingrowth option with using DGA Resin again to collect ⁹⁰Y can be performed. An MDA for ⁹⁰Sr of <1 mBq/L for an 8 h count may be obtained using 10 L seawater sample aliquots.     

Potassium iron(III)hexacyanoferrate(II) supported on polymethylmethacrylate ion-exchanger for removal of strontium(II)

Potassium iron(III)hexacyanoferrate(II) supported on poly metylmethacrylate has been synthesized and investigated for the strontium(II) removal from HNO₃ and HCl solutions. The ion exchange material characterized by different techniques and found to be stable in 1.0–4.0 M HNO₃ solutions, has been used to elaborate different parameters related to ion exchange and sorption processes involved. The data collected suggested its use to undertake removal of Sr(II) from more acidic active waste solutions. Thus the material synthesized had been adjudged to present better chances of application for Sr(II) removal as compared to other such materials.     

Sorption of small amounts of europium(III) on iron(III) hydroxide and oxide

The sorption of small amounts of europium(III) on iron(III) hydroxide and oxide has been studied as a function of pH. The mechanism of sorption is discussed. Optimum conditions have been found for the preconcentration of small or trace amounts of europium(III) by iron(III) hydroxide and oxide. The influence of complexing agents (EDTA, oxalate, tartrate and 5-sulfosalicylic acid) on the sorption of small amounts of europium(III) on iron(III) oxide has also been studied.     

Separation of Y from Sr by zirconium vanadate gel ion-exchanger sorbent: kinetics and thermodynamic study

A new zirconium vanadate (Zr–V) ion-exchanger was synthesized and characterized for fast and selective separation procedure of ⁹⁰Y from ⁸⁹Sr. The method was based on ⁹⁰Y(III) sorption from aqueous HCl solution containing ⁸⁹Sr(II) onto Zr–V gel exchanger. The kinetics of Y(III) sorption from HCl solution by Zr–V exchanger was subjected to Weber–Morris, Lagergren, Bhattacharya and Venkobachar, and Bt models. Initially, the uptake of Y(III) onto the exchanger was fast followed by kinetically first-order sorption with an overall rate constant, K _Lager = (3.55 ± 0.03) × 10^?4 min^?1. Film and intraparticle transport are the two steps that might influence Y(III) sorption. The negative values of ΔG of ⁹⁰Y retention dictate that, the process is a spontaneous. The negative values of ΔH and ΔS reflect the exothermic nature of ⁹⁰Y(IIsorption and the random uptake of ⁹⁰Y(III) onto Zr–V sorbent. Zr–V exchanger offers unique advantages of ⁹⁰Y(III) retention over conventional solid sorbents in rapid and effective separation of traces of ⁹⁰Y(III) from Sr. The exchanger was successfully packed in column for an effective separation of ⁹⁰Y.     

The effect of morphology on the transport of dichloromethane in poly(aryl-ether-ether-ketone)

A study of the transport of the dichloromethane in neat poly(aryl-ether-ether-ketone) (PEEK) samples with thicknesses from 0.08 to 3.0 mm with different morphologies was conducted at 35°C. Both sorption and desorption of the solvent were studied. Thermal annealing was used to vary the sample morphology, and density measurements were used to determine the crystallinity of the samples. The equilibrium concentration of solvent and rate of solvent sorption were found to vary with sample morphology. The density of the dichloromethane when in the PEEK resin was found to be 1.65 g/cm³. Solvent desorption was independent of sample morphology or any previous sample treatment and depended only upon desorption temperature. Solvent sorption appears to alter the morphology of amorphous samples by increasing the crystallinity to about 20% after one sorption/desorption cycle. Small amounts of the solvent, less than 0.5 wt.%, remain trapped in fully desorbed samples. The micromorphology of solvent-induced crystallization appears to be different from that induced by thermal treatment.     

Analytical fractionation of aquatic humic substances by metal affinity chromatography on iron(III)-coated cellulose

The chromatographic fractionation of aquatic humic substances (HS) onto iron(III)-coated cellulose (Cell-Fe(III)) as a metal-loaded adsorbent is described, analogously to the separation principle of the well-established metal affinity chromatography (MAC). For that purpose the sorption of HS from different aquatic origin on that collector was characterized by their kinetics and equilibrium distribution coefficients Kd. Based on Kd values of 10³ to 10⁴,mL/g, and fast sorption kinetics a preparative HPLC procedure, using stepwise increased pH-values (pH 8–12.5, borate buffer) as an eluent, was developed for the fractionation of dissolved HS (up to 7 fractions of different amount). The fractions obtained by this MAC procedure from selected aquatic HS samples were different in their Cu(II) complexation capacity, absorbance ratio E_{265 nm}/E_{365 nm} and Fourier transform infrared spectra. Received: 14 June 1999 / Revised: 6 August 1999 / Accepted: 10 August 1999     

Analytical fractionation of aquatic humic substances by metal affinity chromatography on iron(III)-coated cellulose

The chromatographic fractionation of aquatic humic substances (HS) onto iron(III)-coated cellulose (Cell-Fe(III)) as a metal-loaded adsorbent is described, analogously to the separation principle of the well-established metal affinity chromatography (MAC). For that purpose the sorption of HS from different aquatic origin on that collector was characterized by their kinetics and equilibrium distribution coefficients Kd. Based on Kd values of 10³ to 10⁴,mL/g, and fast sorption kinetics a preparative HPLC procedure, using stepwise increased pH-values (pH 8–12.5, borate buffer) as an eluent, was developed for the fractionation of dissolved HS (up to 7 fractions of different amount). The fractions obtained by this MAC procedure from selected aquatic HS samples were different in their Cu(II) complexation capacity, absorbance ratio E_{265 nm}/E_{365 nm} and Fourier transform infrared spectra. Received: 14 June 1999 / Revised: 6 August 1999 / Accepted: 10 August 1999     

Sorption of Co, Cs, Sr and I onto argillaceous rock as studied by radiotracers</p> </p>

Summary Sorption of⁶⁰Co,⁸⁵Sr, 137Cs and¹²⁵I have been studied on samples originated from Boda (siltstone-) claystone formation (BCF) (Hungary). The distribution of K_dvalues have been determined in static batch experiments using natural groundwater. The order of sorption of isotopes was Co>Cs>Sr>I, where iodine exhibits sorption properties in a modest extent. The sorption isotherm was determined for Cs from measurements carried out in 10^-5-10^-1M initial concentration range. The isotherm can be described with non-linear Freundlich approximation in the range of</o:p></p> 10^-7-10^-4M equilibrium concentration. At concentrations >10^-2M the isotherm achieves saturation. Hence, it is suggested that sorption of Cs on BCF is dominated by cation-exchange reactions on the illite mineral component. In the case of Co and Sr, precipitation reactions occurred during the experiments performed with carrier-containing solutions. This can be attributed to the low values of solubility product constants of SrCO₃, SrSO₄and Co(OH)₂, formed from anions present in the natural groundwater.</p> </p>     

Sorption of chromium(VI) and chromium(III) on aluminium hydroxide

Factors that influence the sorption of Cr(VI) and Cr(III) on aluminium hydroxide were investigated. The sorption of chromates decreases as the pH of the suspension increases. The mechanism of CrO ₄ ^2– sorption was interpreted in terms of reactions between chromates and –OH and/or H₂O groups at the hydroxide/liquid interface. It has been shown that chromates are more tightly sorbed on aluminium hydroxide compared to other anions, e.g. chlorides. On the other hand, specifically absorbed anions, such as molybdates, compete strongly with chromates for the sorption sites. The sorption of chromium(III) increases with the pH of the suspension. Also, the sorption of chromium(III) is suppressed in the presence of citrate ions. The best conditions for the fixation of Cr(VI) and Cr(III) by aluminium hydroxide are presented.     

Determination of Total Iron in Environmental Samples by Solid Phase Extraction with Dimethyl(E)‐2‐(2‐Methoxyphenoxy)‐2‐Butenedioate

A novel solid phase extraction technique for determination of total iron in environmental water samples was developed. The method is based on sorption of Fe(III) ions on octadecyl silica membrane disk modified with a new synthetic ligand dimethyl(E)‐2‐(2‐methoxyphenoxy)‐2‐butenedioate (I). Iron(III) is quantitatively retained on the disk in the pH range of 3–7 at a flow rate of 1–7 mL min⁻¹. The Fe(III) eluted with 10 mL of 0.01 M EDTA and than was measured by flame atomic absorption spectrometry (FAAS) at 248.3 nm. The maximum capacity disk modified by 7 mg of ligand was found to be 197 ± 2 μg of iron(III). The breakthrough volume was greater than 2000 mL. The iron(III) was completely recovered (> 99%) from water with a preconcentration factor of more than 200. The limit of detection of the proposed method was 1.00 ng mL⁻¹. The various cationic and anionic interferences had no effect on the recovery of iron(III) from the binary mixtures. The proposed method was successfully applied to determination of total iron from three different water samples.     

Extraction chromatographic separation of iron from complex liquid samples and the determination of <Superscript>55</Superscript>Fe

Summary Iron separation is described from liquid samples with a high concentration of ions that enables simple determination of ⁵⁵Fe. One of the described methods consists of iron precipitation from a large volume seawater by sodium hydroxide and/or ammonium carbonate and separation from other elements (Ca, Sr, Cu, Mg, etc.) on a TRU column with 4M HCl or 8M HNO₃. In the other procedure iron is separated directly from a mixture of seawater samples and HCl on a TRU column. In both methods, the iron recovery is almost 100%. After separation, ⁵⁵Fe is determined by counting with a liquid scintillation counter. The binding of Fe and Zn on TEVA, U/TEVA and TRU resins from seawater solutions of HCl and HNO₃depends on the type of the resin, concentration of acid and other ions. Iron and zinc can be separated from seawater on a U/TEVA column with 2M HCl.     

Sorptionseffekte an Eisen(III)-hydroxid-F?llungen

Zusammenfassung Um Material zur Deutung des Mechanismus der Sorption von Sr²⁺-Ionen an Eisen(III)-hydroxid zu gewinnen, werden Meßreihen mitgeteilt, in denen die pH-Abhängigkeit der Sorption sowie deren Beeinflussung bei Fällung mit verschiedenen Basen (NaOH, Ammoniak, Trimethylamin, Benzylamin) untersucht wird. Aus den charakteristischen Unterschieden der Sorptionskurven muß gefolgert werden, daß die Art der Base für die Sorption eine wichtige Rolle spielt.

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Summary The sorption of Sr²⁺ ions on iron(III) hydroxide was studied as a function of the pH, of the precipitating reagent (NaOH, ammonium hydroxide, benzylamine, trimethylamine), of the temperature and of the total concentration.The curves of the relative sorption vs. pH are found to show characteristic differences which have to be explained in a detailed theory of the mechanism.

     

Sorption of rare earth elements of waste solution of leaching uranium

The possibility of sorption recovery of rare earth elements from the waste sulfate solutions of uranium leaching, which contain a few tens of milligrams per liter of the rare earth elements, up to 1 g L^?1 of aluminum, and 2 g L^?1 of iron, with using a carboxyl sorbent CYBBER LX 280, hydrated titanyl hydrogen phosphate and its analogue modified with zirconium(IV). It was shown that 95% of the rare earth elements and more can be recovered by neutralizing the solution by sodium hydroxide to pH ≈ 4.2, separating the resulting precipitate based on iron hydroxide, and subsequent sorption at the CYBBER LX 280 sorbent.     

Synthesis of arsenic sorbent by the reaction of magnesium hydroxide with aqueous iron(III) chloride solution

The reaction of magnesium hydroxide with a concentrated aqueous solution of iron(III) chloride yields a mixture of magnesium–iron layered double hydroxide and iron oxide–hydroxide in the akaganeite form. The content of these phases depends on the Mg/Fe atomic ratio in the starting reactant mixture. Iron oxide–hydroxide is the major reaction product at the Mg/Fe atomic ratio in the interval 1.5–1.75, and layered magnesium–iron layered double hydroxide, at Mg/Fe = 3–4. The ability of the synthesized products to take up As(III) from aqueous solutions was studied. These sorbents allow the arsenic concentration to be decreased from 3–5 mg L^–1 to values below MPC (0.01 mg L^–1).     

Determination of sorption capacity of fucoidic sands for Cs+ and Sr2+ under dynamic column conditions

In this paper, the sorption behavior of Cs⁺ and Sr²⁺ on column of fucoidic sands under dynamic flow conditions was investigated, and their sorption capacities (SC) towards these two cations were studied. The determination of SC is based on the construction of respective breakthrough curves using ¹³⁷Cs and ⁸⁵Sr radionuclides as isotopic indicators in laboratory experiments. The samples were taken from several parts of the borehole in the area of interest. Undisturbed cores of 5 cm in diameter and 10 cm long were put in the glass columns and the cores were perfectly tightened using acrylate resin. In this time-dependence study, the so-called cenoman background groundwater was used. A concentration of 10^?6 mol/dm³ of Cs⁺ and Sr²⁺ in liquid phase individually was established using neutral salts of CsNO₃ and Sr(NO₃)₂, respectively. The groundwater was introduced at the bottom of the columns by a multi-head peristaltic pump, at a constant flow-rate of about 4 cm³/h. The results show that the sorption capacity of the investigated fucoidic sands for ¹³⁷Cs and ⁸⁵Sr is 0.1–1.5 and 0.05–0.5 μmol/100 g, respectively, in dependence on the evaluation of corresponding breakthrough curves. Some differences in the behavior of the cores during the experiments have also been observed and explained.     

Flow-injection determination of total iron in freshwater samples with neutralisation chemiluminescence

A flow-injection chemiluminescence method has been established for the determination of total iron in freshwater samples. The enhanced chemiluminescence emission was caused by the iron(II) from the neutralisation reaction of hydrochloric acid and sodium hydroxide without the use of any chemiluminescent reagent. The calibration graph was linear in the concentration range of 2.8–560 µg L^?1 (r ² = 0.9983, n = 8), with relative standard deviation (RSD; n = 4) in the range of 0.8–2.6%. The limit of detection (S/N = 3) was 0.56 µg L^?1 with injection throughput of 180 h^?1. The effect of common anions and cations were studied over their environmentally relevant concentrations in freshwaters. The method was successfully applied to determine total iron in freshwater samples. Iron(III) was reduced to iron(II) by using hydroxylammonium chloride. The proposed method was compared with spectrophotometric method and there was no significant difference between the two methods at the 95% confidence level (t-test). Analysis of river water (certified reference material SLRS-4) for iron(II), after reduction of iron(III) with hydroxylammonium chloride, gave good results (2.17 ± 0.22 µM compared with the certificate value of 1.85 ± 0.1 µM).     

Sensitive determination of iron(III) by gold electrode modified with 2-mercaptosuccinic acid self-assembled monolayer

Preparation and application of gold 2-mercaptosuccinic acid self-assembled monolayer (Au-MSA SAM) electrode for determination of iron(III) in the presence of iron(II) is described by cyclic voltammetry, electrochemical impedance spectroscopy, and Osteryoung square wave voltammetry. The square wave voltammograms showed a sharp peak around positive potentials +0.250 V that was used for construction of the calibration curve. Parameters influencing the method were optimized. A linear range calibration curve from 1.0 × 10⁻¹⁰ to 6.0 × 10⁻⁹ M iron(III) with a detection limit of 3.0 × 10⁻¹¹ M and relative standard deviation (R.S.D.) of 6.5% for n = 8 at 1.0 × 10⁻⁹ M iron(III) was observed in the best conditions. Possible interferences from the coexisting ions were also investigated. The results demonstrated that sensor could be used for determination of iron(III) in the presence of various ions. The validity of the method and applicability of the sensor were successfully tested by determining of iron(III) in natural waters (tap and mineral waters) and in a pharmaceutical sample (Venofer^® ampoule) without interference from sample matrix. The experimental data are presented and discussed from which the new sensor is characterized.