Determination of Hf, Sc and Y in geological samples together with the rare-earth elements

 A method is described for the determination of Hf, Sc and Y simultaneously with the REE in geological materials. An earlier method for REE separation from major elements was studied with the aim to apply it also to the determination of Hf, Sc and Y. Sample decomposition was carried out by melting with LiBO₂. The method involves separation and concentration stages, using the cation-exchange resin DOWEX AG 50W-X8. Matrix elements were eluted with 2 mol/l HCl, whereas 6 mol/l HNO₃ with oxalic acid and 8 mol/l HNO₃ were used to elute the elements to be determined. Some of the matrix elements could not be completely removed. This effect as well as the recovery rates of the determined elements were investigated. The measurements were performed by ICP-AES. Spectral interferences were also tested. Received: 8 November 1995/Revised: 12 March 1996/Accepted: 14 March 1996     

Inductively coupled plasma atomic emission spectroscopic determination of rare earth elements in geological samples after preconcentration by countercurrent chromatography—Part II

This paper directly links up with Part I [Spectrochim. Acta 48B, 1365 (1993)] which treats the first application of countercurrent chromatography (CCC) for pre-separation of rare earth elements (REE) in rocks. The rapid and reliable separation and pre-concentration of “light” REE and Y can be achieved using a system of 0.5 mol/l di-2-ethylhexylphosphoric acid (D2EHPA) in n-decane-hydrochloric acid of different concentrations and a planetary centrifuge as a CCC device. However, Tm, Yb and Lu are partially retained in the stationary phase. Comparative data is presented on three other two-phase liquid systems containing trioctylphosphine oxide (TOPO); D2EHPA and TOPO mixtures and diphenyl(dibutylcarbamoylmethylphosphine)oxide (Ph₂-Bu₂) as extractants in terms of their ability for whole REE group complete isolation from the rock constituents. The partial losses of “light” REE (La and Ce) occurred in the system of 0.1 mol/l solution of TOPO in isobutylmethylketone (IBMK) (stationary phase)-1 mol/l NH₄NO₃-6 mol/l HCl aqueous solutions (mobile phase). Complete isolution of the entire REE group can be reached in two systems: 0.3 mol/l D2EHPA + 0.02 ml/l TOPO in the solvents mixture (3:1) of n-decane + IBMK, respectively (stationary phase)-1 mol/l NH₄NO₃-6 mol/l HCl aqueous solution (mobile phase), and 1.0 mol/l Ph₂-Bu₂ solution in chloroform (stationary phase)-3 mol/l HNO₃ aqueous solution (mobile phase). The D2EHPA + TOPO mixture is recommended as more economic and accessible.     

Preconcentration of rare earths in geological materials with ascorbic acid for their neutron activation analysis

The potential use of ascorbic acid as a complexing reagent in the separation and preconcentration of rare earth elements (REE) in geological materials in a suitable solid matrix has been demonstrated. Traces of REE from some USGS standard rock samples, viz., GSP-1, G-2, AGV-1 and PCC-1, have been separated after acid dissolution in two ways: (1) by ion exchange chromatography on Dowex 50×8 column and Na-ascorbate as eluent and (2) by direct complexation with ascorbic acid under specific experimental conditions. The separated REE were coprecipitated with the non isotopic diluent, calcium fluoride, before neutron activation analysis. Radiometric determinations showed that the overall recovery of REE in both cases was practically quantitative.     

Determination of phenoxyacid herbicides in water

Novel clean-up techniques for a polymeric precolumn (PLRP-S) for the subsequent determination of bentazone and eight phenoxy acid herbicides in surface water samples are described. After preconcentration of the components at pH 3 on a 10 x 2 mm I.D. precolumn, the technique consists of a clean-up with 1000 microliters of 0.1 mol/l sodium hydroxide solution (pH 12.5) and of a heartcut consisting of four precolumn bed volumes of eluent directed to waste followed by ten precolumn bed volumes of eluent directed to the analytical column. Analytical separation is performed with acetonitrile-water (30:70) containing 0.005 mol/l of tetrabutylammonium hydrogensulphate (pH 8.3) (which is also the desorption eluent during heartcutting) on a polymeric analytical column (PLRP-S). With 25 ml of surface water, spiked at 0.25 and 1 microgram/l, applied to the precolumn, recoveries for all components were over 85% with a relative standard deviation (n = 5) of ca. 9% at 0.25 microgram/l and ca. 2% at 1 microgram/l. Detection limits in surface water samples are 0.05-0.1 microgram/l. Owing to automation, the total analysis time is ca. 30 min.     

Simultaneous determination of silicon and phosphorus in biological standard materials with on-line column flow-injection spectrophotometry

Summary A simultaneous determination of silicon and phosphorus in biological standard materials with on-line column flow-injection spectrophotometry (FIA) is described. Biological materials are ashed, fused with a lithium carbonate-boric acid mixture, and dissolved in a hydrochloric acid solution. Interfering cations are removed by a simple cation-exchange column filtration. The acid effluent is evaporated to dryness, fused with a small amount of sodium carbonate for depolymerization, taken up in dilute EDTA solution, and analyzed for silica and phosphorus by FIA. For the simultaneous determination of these elements, TSK-gel SAX was used, and the eluent was 0.085 mol/l NaCl/0.01 mol/l NH₃/0.001 mol/l EDTA. Several standard reference materials [bovine liver (NBS), chlorella and pepperbush (NIES)] were analyzed for both elements. The results of phosphorus determination for bovine liver are in satisfactory agreement with the NBS certificated value. ICP measurements were applied to analyses of chlorella and pepperbush for silica and phosphorus. The agreement of the analytical results between FIA and ICP is satisfactory. Silica in bovine liver was determined in the present study for the first time.

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Simultanbestimmung von Silicium und Phosphor in biologischen Standardmaterialien mit Hilfe von On-line Fließinjektions-Spektralphotometrie

     

Fluorometric Determination of Tryptophan and Its Brain Indoleamine Metabolites by Ion-Pair HPLC

Abstract

The reverse phase HPLC separation of tryptophan, serotonin, 5-hydroxyindoleacetic acid, tryptamine and indoleacetic acid using two solvent systems (one of them containing an ion-pairing reagent) is reported. The two low concentration eluents employed are either formic acid/water or 0.005 mol/L solution of 1-pentane sulfonn ic acid. In both cases chromatographic separation was achieved through a linear gradient elution using methanol/water (7/3) as the high concentration eluent. We also describe the variation of retention volumes of these compounds as a function of the pH of the mobile phase. pH values ranged from 1.5 to 4.0 and were obtained by adding either formic acid or NaOH respectively to the low concentration eluent. Tryptophan and its metabolites were detected fluorometrically. All compounds show a linear response in the pg to μg range. The chromatographic separation achieved allows a concurrent measurement of tryptophan and its main indoleamine metabolites which coupled to the high sensitivity of fluorometric detection permits a direct estimation of these metabolic pathways in brain tissue.     

Cation-exchange isolation and ICP-AES determination of rare earth elements in geological silicate materials

An ion-exchange ICP-AES method for the determination of 14 rare earth elements (REEs) and Y in geological materials is described. The separation of REEs from Ba using a Dowex 50W-X8 cation resin is especially considered since Ba is an excellent internal standard for REE determination by this technique. Although total recovery with either HCl or HNO₃ may be achieved, it is advantageous to use both acids sequentially. Volume and concentration of the acids are optimized attaining a quantitative separation of REEs from Ba by the introduction of the sample solution in a 1.75 mol/l HCl medium, followed by elution with 2 mol/l HNO₃ to remove matrix elements and with 7 mol/l HNO₃ to elute the analytes. The total elution volume is significantly reduced without decreasing the efficiency. The behaviour of the matrix constituents under the selected conditions is also studied, evaluating their elution percentages in each step. The final solution obtained contains only the REEs and Y, with the bulk of Sc and minor amounts of Cr, Fe, Hf and Ta. Experimental data for 5 geological reference standards (NIM-G, GSP-1, AGV-1, NIM-L and NIM-S) are reported. Good agreement between the present results and previously accepted values by various analytical techniques is observed.     

The chromatographic interaction and separation of metal ions with 8-Quinolinol stationary phases in several aqueous eluents

Several 8-quinolinol silica gel (QSG) columns were used, with metal-uptake capacities of 10–156 μmol g^?1. Various transition and heavy metal ions were used as analytes in nitrate, sulfate, phosphate, citrate, tartrate, oxalate, phthalate, and maleate mobile phases. Metal-ion retention increased with column capacity and pH. Optimum capacity factors were obtained on columns of intermediate capacity (27 and 46 μmol g^?1). Retention times decreased with an increase in eluent buffer concentration, typically by half with a doubling of buffer. Evidence is presented for the occurence of mobile-phase complexation of analyte ions by eluent buffer species. Multiple or split peaks were often observed when the analyte solvent differed from the mobile phase. Chromatographic separation of up to six metals on the QSG columns is demonstrated in tartrate and maleate mobile phases.     

Simultaneous determination of mono- and bivalent cations in environmental chemistry using isocratic ion chromatography

Summary The influence of the pH of the mobile phase ethylenediamine (EDA)/citrate on the retention behaviour of mono- and bivalent cations on a silica based cationexchange stationary phase was studied. Variation of the pH-value was accomplished either by changing the concentration of one component of the eluent or by adding potassium hydroxide or hydrochloric acid to an eluent of fixed composition. The pH range between 2.8 and 3.0 proved to be most suitable for the separation of mono- and bivalent cations. Alkali metals, alkaline earths and transition elements could be separated in a single run. Extending the pH-range up to 5.2 showed the possibility of an additional determination of more strongly retained ions, such as Pb²⁺ or Sr²⁺.

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Simultanbestimmung ein- und zweiwertiger Kationen in der Umweltchemie mit Hilfe der isokratischen Ionen-Chromatographie

     

High-performance liquid chromatography with post-column reaction detection for the determination of rare-earth elements in phosphoric acids produced for the manufacture of phosphate fertilizers

The isolation of rare elements (REE) from technical phosphoric acids and their determination by h.p.l.c. with post-column reaction detection are examined with different liqiud chromatographic techniques. A combination of procedures provides optimum analytical conditions. Twelve REE can be separated within 20 min by applying the following procedures: (i) separation of REE from calcium by addition of ammonium pyrrolidinedithiocarbamate to the sample solution, passage through a disposable column (SepPak C18), and use of dilute perchloric acid for desorption; (ii) separation of REE by using a chemically bonded strong cation-exchanger (Servachrom Si-100) and gradient elution with α-hydroxyisobutyric acid. The performance of this combination is discussed in relation to the restrictions imposed by the post-column reaction detector based on complexation with 4-(2-pyridylazo) resorcinol. Results obtaiend for two types of technical phosphoric acid are presented.     

Precise determination of rare earth elements in rocks by neutron activation analysis

A pre-irradiation group separation method has been developed for the neutron activation analysis of rare earth elements (REE) and Ba in silicate rocks. REE and Ba were quantitatively separated from other elements by cation exchange column method. The chemical yield of each separation was monitored with Pr added to the sample powder before decomposition. The accuracy and precision were tested by repeated analyses of JB-1 and one analysis of BCR-1. In addition, it was found that REE distribution in a granitic rock powder was inhomogeneous and therefore special care must be taken for the sampling of granitic rock powders.     

Determination of rare earth elements in USGS rock standards by isotope dilution mass spectrometry and comparison with neutron activation and inductively coupled plasma atomic emission spectrometry

Rare earth element (REE) concentrations in United States Geological Survey (USGS) rock standards AGV-1, GSP-1, G-2 and PCC-1 were determined by isotope dilution mass spectrometry (IDMS), neutron activation and inductively coupled argon plasma atomic emission spectrometric techniques. The procedure involved acid digestion of samples in PTFE pressure bombs and group separation of REEs by an ion-exchange method. For IDMS an additional separation step using α-hydroxyisobutyric acid as an eluent was used in a cation-exchange column to split the REEs into subgroups. Comparison of the results with literature values showed that the IDMS values are the most precise and accurate. However, the precisions and the accuracies of the other techniques are acceptable.     

Investigation of the separation of scandium and rare earth elements from red mud by use of reversed-phase HPLC

A chromatographic method has been developed for separation and determination of scandium (Sc) and rare earth elements (REEs) in samples from a red mud (RM)-utilization process. Reversed-phase high-performance liquid chromatography (RP-HPLC) with post-column derivatization using 4-(2-pyridylazo)-resorcinol (PAR) and UV–visible detection at 520 nm was tested using different gradient elution profiles and pH values to optimize separation and recovery, primarily for Sc but also for yttrium and the individual lanthanides, from iron present in the samples. The separation was performed in less than 20 min by use of a mobile phase gradient. The concentration of -hydroxyisobutyric acid (-HIBA), as eluent, was altered from 0.06 to 0.4 mol L^–1 (pH 3.7) and 0.01 mol L^–1 sodium salt n-octane sulfonic acid (OS) was used as modifier. Very low detection limits in the nanogram range and a good resolution for Sc and REEs except for Y/Dy were achieved. Before application of the method to the red mud samples and to the corresponding bauxites, Sc and REEs were leached from red mud with 0.6 mol L^–1 HNO₃ and mostly separated, as a group, from the main elements by ion exchange/selective elution (6 mol L^–1 HNO₃) in accordance with a pilot-plant process developed in this laboratory. After evaporation of the eluent to dryness the extracted elements were re-dissolved in the mobile phase. By use of this chromatographic method Sc, which is the most expensive of the elements investigated and occurs in economically interesting concentrations in red mud, could be separated not only from co-existing Fe but also from Y/Dy, Yb, Er, Ho, Gd, Eu, Sm, Nd, Pr, Ce and La. All the elements investigated were individually recovered. Their recoveries were found to be nearly quantitative.     

有机酸在阴离子交换树脂上的保留行为及其机理

研究了有机酸在阴离子交换树脂上的保留行为。首次报道了有机酸在阴离子交换色谱过程中的“多峰现象”,即一种有机酸有两个或两个以上的色谱峰流出色谱柱。对这种“多峰现象”形成的机理进行了初步探讨,提出了有机酸离解后的不同价数阴离子在阴离子交换树脂上同时保留的机理。研究中还发现离解很弱的有机酸的保留行为不完全符合离子交换机理。     

Separation of rare earth and transplutonium elements by displacement chromatography on KU-2 cation exchange resin in the Cu2+ form under ionizing radiation

Changes in chromatographic parameters (pH, REE concentration, eluent concentration, separation coefficients) under irradiation using the KU-2 cation exchange resin in the Cu²⁺ form are studied experimentally and theoretically depending on the absorbed dose and respective destruction of the eluent. It is found that the use of the cation exchange resin in the Cu²⁺ form in the field of ionizing radiation leads to a more effective separation of REEs than in the case of using the Zn²⁺ and H⁺ forms of cation exchange resin.     

Ion-exclusion/adsorption chromatography of dimethylsulfoxide and its derivatives for the evaluation to quality-test of TiO(2)-photocatalyst in water

Ion-exclusion/adsorption chromatography of dimethylsulfoxide (DMSO) and its derivatives, i.e., methanesulfinic acid (MSI), methanesulfonic acid (MSA) and sulfuric acid (SA), was developed in order to clear the decomposition mechanism of DMSO on quality-test of TiO₂-photocatalyst in water. The separation was achieved by the adsorption effect for DMSO and ion-exclusion effect for MSI, MSA and SA under optimum conditions, using a weakly acidic cation-exchange resin column with 20 mM succinic acid as the eluent. In this system, DMSO and MSI with UV at 195 nm and MSA and SA with conductivity detection were consecutively determined by single injection and single separation column. This method was used to monitor the artificial decomposition of DMSO induced by a photocatalyst. The concentration of DMSO by active oxygens (e.g., OH radical) generated from surface of photocatalyst was found to be decreased through the stoichiometric reaction in the order of MSI, MSA and SA.     

Ion chromatography of nitrite and carbonate in inorganic matrices on an octadecyl—poly(vinyl alcohol) gel column using acidic eluents

Low levels of carbonate and nitrite contained in inorganic matrices were determined by ion chromatography on an Asahipak ODP-50 poly(vinyl alcohol) gel-based reversed-phase column. With an acidic mobile phase, inorganic matrix anions and cations eluted near the void volume of the column, whereas carbonate and nitrite were retained and separated completely from the matrix ions. After the separation column, the peak response was enhanced using a cation-exchange hollow fibre and 25 mM sodium sulphate or alkaline enhancers. Sea-water samples can be applied directly for the determination of carbonate and added nitrite at ppm levels. The maximum sample volume that can be loaded on the column without peak deformation depended on the pH of the sample solution and the sulphuric acid concentration in the eluent. A 50 μl sea-water sample was applicable with a 2.5 mM acid eluent.     

Use of Microspherical Sulfonated Hypercrosslinked Polystyrene in Ion Chromatography

The possibility of applying sulfonated cation exchangers on the basis of hypercrosslinked polystyrene (HCPS) of different ion-exchange capacity for the ion-chromatographic separation of alkali metal and ammonium cations was demonstrated. The effect of the nature and concentration of the eluent, the temperature of the chromatographic column, additions of an organic solvent to the eluent, and the ion-exchange capacity of the sorbent on the retention of cations was examined. An unusual selectivity of the sorbent for lithium and ammonium cations was found; the elution order can change for the Li⁺/Na⁺ and Rb⁺/NH⁺ ₄ pairs depending on the nature of the eluent, the temperature, additions of an organic solvent, and the structural characteristics of the sorbent. When dilute solutions of nitric acid are used as the eluent, the following elution order of cations was obtained: Na⁺ < Li⁺ < K⁺ < NH⁺ ₄ < Rb⁺ < Cs⁺ Mg²⁺ < Sr²⁺ < Ca²⁺ < Ba²⁺. Under the optimum conditions of separation (1 mM solution of sulfuric acid, 20°C) on sulfonated HCPS with an ion-exchange capacity of 0.07 mequiv/g, the separation of ammonium and alkali metal cations was achieved within 17 min.     

Solvent extraction of tricyclic amines from blood plasma and liquid chromatographic determination

The extraction of seven tricyclic antidepressant amines from human plasma at different pH values was investigated for dichloromethane, diethyl ether and hexane--1-pentanol (95:5). The amines were extracted as bases and back-extracted to sulphuric acid, 0.10 mol/l, prior to the separation by bonded-phase liquid chromatography. Ether and hexane--1-pentanol (95:5) were most suitable, tertiary amines being best extracted at pH 8, and secondary amines at pH 10. Using ether, both while 15 min ws sufficient for hexane--1-pentanol (95:5). UV detection allowed concentrations down to 10 ng in 1 ml of plasma to be determined. Three ammonium ions--octylammonium, dimethylammonium, and trimethylammonium--were added as modifiers to the mobile phase containing acetonitrile in phosphoric acid, 0.10 mol/l. In the concentration interval 0.010--0.030 mol/l all of the amine modifiers gave on Polygosil C8 peak asymmetry factors of sufficiently low magnitude, while on Li-Chrosorb RP-18 this was so only for di- and trimethylammonium in a concentration of 0.030 mol/l.     

Speciation of rare earth elements in soil by sequential extraction then HPLC coupled with visible and ICP-MS detection

The distribution of rare earth elements (REE) in a pooled soil sample collected from Zhangzhou, Fujian Province, China, was screened by a five-step sequential extraction procedure coupled with ICP–MS determination after preconcentration of REE and removal of the matrix by extraction with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP). The results showed that the distribution of REE in the different fractions of the pooled soil sample studied followed the order soluble species (46.76%) > species bound to organic matter (22.08%) > species in the residue (16.77%) > species bound to Fe–Mn oxides (2.02%). An effective method for speciation of REE, which utilized weak cation-exchange HPLC separation hyphenated with post-column derivatization and visible or on line ICP–MS detection, was, moreover, developed and successfully applied to the speciation of REE in the soluble extract of the pooled soil sample. The stability of known complexes of lanthanum during the HPLC separation was investigated with fluoride, citrate, and ethylenediamine tetraacetic acid (EDTA) chosen as ligands modeling those in the soil. REE in the soluble extract of the pooled soil sample were subsequently classified into three types of species –≤ + 1 charged complexes (negatively charged, neutral, and +1 charged), + 2 charged complexes, and “free” REE species. This method is expected to be useful for identification of bioavailable (or toxic) species of REE in environmental samples. Received: 14 November 2000 / Revised: 26 January 2001 / Accepted: 30 January 2001