Collection of trace metals with cationic surfactant-silica particles followed by flotation with an anionic surfactant for seawater analysis.

The analysis of seawater for trace metals is important for pollution monitoring and better understanding of marine systems. The present paper describes an efficient preconcentration method for the determination of trace metals in seawater. Trace metals [Ni(II), Cu(II), Ga(III), Cd(II), Pb(II), and Bi(III)] in 1,000 mL of seawater sample were complexed with ammonium pyrrolidinedithiocarbamate and sorbed onto silica particles covered with cetyltrimethylammonium chloride. After the addition of sodium dodecyl sulfate, the particles were floated to the solution surface by bubbling and then collected by suction. The trace metals were desorbed with dilute nitric acid and determined by inductively coupled plasma-mass spectrometry. The rapid 200-fold preconcentration was demonstrated with certified seawater samples.

Phosphoester hydrolysis by cerium(IV)-thiacalix[4]arene complexes and its application to immunoassay.

Thiacalix[4]arenetetrasulfonate was treated with Ce(IV) in water at pH 9.5 to give novel phosphoester-hydrolyzing complexes. The dinuclear Ce(IV) complex promoted the hydrolysis of p-nitrophenyl phosphate with a turnover frequency of 6.8 h(-1) at 50 degrees C, showing fourfold higher activity than the mononuclear complex. The dinuclear complex was readily immobilized onto an antibody by simply mixing them in water, hence its phosphatase-like activity was applied to the color-developing reaction in immunoassay. The model assay using an antibody labeled with the dinuclear complex allowed the detection of as little as 10 ng mL(-1) of a tumor marker, Bence-Jones protein, in a 96-well microtiter plate format. Analysis of urine for Bence-Jones protein was performed by the proposed method.

Sulfinylcalix[4]arene-impregnated amberlite XAD-7 resin for the separation of niobium(V) from tantalum(V).

Amberlite XAD-7 resin was impregnated with p-tert-butylsulfinylcalix[4]arene. Niobium(V) was collected on the impregnated resin in yields of more than 90% around pH 5.4, whereas tantalum(V) was negligibly collected. The collected niobium(V) was desorbed with 9 M sulfuric acid nearly quantitatively, hence the separation of niobium(V) from tantalum(V) was successfully achieved.

Ionic liquid-based extraction followed by graphite-furnace atomic absorption spectrometry for the determination of trace heavy metals in high-purity iron metal.

The analysis of high-purity materials for trace impurities is an important and challenging task. The present paper describes a facile and sensitive method for the determination of trace heavy metals in high-purity iron metal. Trace heavy metals in an iron sample solution were rapidly and selectively preconcentrated by the extraction into a tiny volume of an ionic liquid [1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] for the determination by graphite-furnace atomic absorption spectrometry (GFAAS). A nitrogen-donating neutral ligand, 2,4,6-tris(2-pyridyl)-1,3,5-triazine (TPTZ), was found to be effective in the ionic liquid-based selective extraction, allowing the nearly complete (~99.8%) elimination of the iron matrix. The combination with the optimized GFAAS was successful. The detectability reached sub-µg g(-1) levels in iron metal. The novel use of TPTZ in ionic liquid-based extraction followed by GFAAS was successfully applied to the determination of traces of Co, Ni, Cu, Cd, and Pb in certified reference materials for high-purity iron metal.

Separation of Gd-humic complexes and Gd-based magnetic resonance imaging contrast agent in river water with QAE-Sephadex A-25 for the fractionation analysis.

Gadolinium complexed with naturally occurring, negatively charged humic substances (humic and fulvic acids) was collected from 500 mL of sample solution onto a column packed with 150 mg of a strongly basic anion-exchanger (QAE-Sephadex A-25). A Gd-based magnetic resonance imaging contrast agent (diethylenetriamine-N,N,N',N″,N″-pentaacetato aquo gadolinium(III), Gd-DTPA(2-)) was simultaneously collected on the same column. The Gd-DTPA complex was desorbed by anion-exchange with 50mM tetramethylammonium sulfate, leaving the Gd-humic complexes on the column. The Gd-humic complexes were subsequently dissociated with 1M nitric acid to desorb the humic fraction of Gd. The two-step desorption with small volumes of the eluting agents allowed the 100-fold preconcentration for the fractionation analysis of Gd at low ng L(-1) levels by inductively coupled plasma-mass spectrometry (ICP-MS). On the other hand, Gd(III) neither complexed with humic substances nor DTPA, i.e., free species, was not sorbed on the column. The free Gd in the effluent was preconcentrated 100-fold by a conventional solid-phase extraction with an iminodiacetic acid-type chelating resin and determined by ICP-MS. The proposed analytical fractionation method was applied to river water samples.

Solid-phase extraction followed by HPLC for the determination of phosphorus(V) and arsenic(V).

Traces of P(V) and As(V) in sample solutions were converted into heteropoly molybdic acids at pH 1.5 and collected onto polyoxyethylene(20)-4-isononylphenoxy ether-coated Amberlite XAD-4 particles. The desorption was carried out with 0.3 M tetramethylammonium hydroxide solution for the HPLC analysis. Molybdophosphoric and molybdoarsenic acids were separated from excess molybdate by ion-pair reversed phase HPLC, though the peaks of P(V) and As(V) could not be resolved. However, the selective decomposition of molybdoarsenic acid with citric acid allowed the differential determination of P(V) and As(V) at the ng mL(-1) level. The proposed method was applied to the analysis of high-purity iron for P and As.

Determination of trace impurities in high-purity iron using salting-out of polyoxyethylene-type surfactants.

To an iron sample solution was added polyoxyethylene-4-isononylphenoxy ether (PONPE, nonionic surfactant, average number of ethylene oxides 7.5) and the surfactant was aggregated by the addition of lithium chloride. The iron(III) matrix was collected into the condensed surfactant phase in >99.9% yields, leaving trace metals [e.g., Ti(IV), Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II), and Bi(III)] in the aqueous phase. After removing the surfactant phase by centrifugation, the remaining trace metals were concentrated onto an iminodiacetic acid-type chelating resin. The trace metals were desorbed with dilute nitric acid for the determination by inductively coupled plasma-mass spectrometry or graphite-furnace atomic absorption spectrometry. The proposed separation method allowed the analysis of high-purity iron metals for trace impurities at low microg g(-1) to ng g(-1) levels.

Admicelle-mediated collection followed by flotation for the preconcentration of trace metals in fresh waters.

Dithizone-impregnated admicelles were prepared by mixing silica particles with dithizone and cetyltrimethylammonium chloride in 0.1 mol L(-1) aqueous ammonia. The resulting admicelles were added to 1000 mL of sample solution and dispersed by stirring for 15 min. Traces of Ni(II), Cu(II), Ga(III), Cd(II), Pb(II) and Bi(III) in the solution were simultaneously incorporated into the admicelles at pH 7.5-9. With the aid of a rising stream of numerous tiny bubbles, the admicelles were floated on the solution surface and collected in a small sampling vessel by suction. The metals were desorbed from the admicelles with dilute nitric acid and determined by inductively coupled plasma-mass spectrometry. The proposed method offered a 100-fold multielement preconcentration and it was applicable to the analysis of river and pond waters.

Redox-driven transport of copper ions in an emulsion liquid membrane system.

A new redox-driven type of emulsion liquid membrane separation is described. Milligram amounts of copper(II) in 0.2 M hydrochloric acid were reduced to copper(I) in the presence of ascorbic acid (1 M identical with 1 mol l(-1)). The copper solution was emulsified with a (1+4) mixture of toluene and n-heptane using Span-80 (sorbitan monooleate) as an emusifier. The resulting water-in-oil emulsion was dispersed in 0.2 M hydrochloric acid containing hydrogen peroxide and neocuproine (2,9-dimethyl-1,10-phenanthroline) by stirring for 10 min. The copper in the internal aqueous phase was selectively transported to the external one, leaving other heavy metals (e.g., Mn, Co, Ni, Cd and Pb) in the internal aqueous phase. After collecting the dispersed emulsion globules, they were demulsified by heating and the metals in the segregated aqueous phase were determined by graphite-furnace atomic absorption spectrometry (GFAAS). The selective transport of copper offered the multielement separation of trace heavy metals from a copper matrix, allowing the GFAAS determination of impurities at the 0.01% level in copper metal.

Removal of an iron matrix with polyoxyethylene-type surfactant-coated amberlite XAD-4 for the determination of trace impurities in high-purity iron.

Admicellar sorbents for the removal of an iron matrix were prepared for the determination of trace impurities in high-purity iron. A 1.0-g amount of Amberlite XAD-4 (macroreticular styrene-divinylbenzene copolymer) was coated with 0.14-1.3 mmol of polyoxyethylene-type surfactants, including polyoxyethylene-4-tert-octylphenoxy ethers (Triton X series) and polyoxyethylene-4-isononylphenoxy ethers (PONPEs). The surfactant-coated XAD-4 was packed into a polypropylene column (7 mm i.d. x 50 mm high). A 5.0-cm(3) volume of sample solution was passed through the column at a flow rate of 0.5 cm(3) min(-1). Milligram amounts of iron(III) were effectively sorbed on the column from 8 mol dm(-3) hydrochloric acid solutions. Among the surfactants tested, polyoxyethylene(20)-4-isononylphenoxy ether (PONPE-20) showed the best performance: the iron leaked from the PONPE-20 column was 4 microg when 25 mg of iron(III) was introduced onto the column. Trace elements, such as Ti(IV), Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Ag(I), Cd(II), Pb(II), and Bi(III), were not retained on the column and thus quantitatively recovered in the column effluent. The effective separation of trace elements from an iron matrix allowed their accurate determinations by inductively coupled plasma-mass spectrometry or graphite furnace atomic absorption spectrometry. The detection limits (3sigma blank) were in the nanogram per gram range. The proposed method was successfully applied to the determination of trace impurities in high-purity iron samples.

Selective determination of beryllium(II) ion at picomole per decimeter cubed levels by kinetic differentiation mode reversed-phase high-performance liquid chromatography with fluorometric detection using 2-(2'-hydroxyphenyl)-10-hydroxybenzo[H]quinoline as precolumn chelating reagent.

A highly sensitive and selective method for the determination of the Be(II) ion has been developed by the use of reversed-phase high-performance liquid chromatography (HPLC) with fluorometric detection using 2-(2'-hydroxyphenyl)-10-hydroxybenzo[h]quinoline (HPHBQ) as a precolumn (off-line) chelating reagent. The reagent HPHBQ has been designed to form the kinetically inert Be chelate compatible with high fluorescence yield, which is appropriate to the HPLC-fluorometric detection system. The Be-HPHBQ chelate is efficiently separated on a LiChrospher 100 RP-18(e) column with a methanol (58.3 wt %)-water eluent containing 20 mmol kg(-1) of tartaric acid and is fluorometrically detected at 520 nm with the excitation at 420 nm. Under the conditions used, the concentration range of 20-8,000 pmol dm(-3) of Be(II) ion can be determined without interferences from 10 micromol dm(-3) each of common metal ions, typically Al(III), Cu(II), Fe(III), and Zn(II), and still more coexistence of Ca(II) and Mg(II) ions at 0.50 mmol dm(-3) and 5.0 mmol dm(-3), respectively, is tolerated. The detection limit (3a baseline fluctuation) is 4.3 pmol dm(-3) (39 fg cm(-3)). The extraordinarily high sensitivity with toughness toward the matrix influence was demonstrated with the successful application to environmental Be analyses, such as determination of Be in rainwater and tap water.

Separation of traces of heavy metals from an iron matrix by use of an emulsion liquid membrane.

An emulsion liquid membrane method has been developed for separating traces of heavy metals from an iron matrix. A 1.0-mL volume of aqueous iron(III) solution (pH 2.0) was emulsified with a mixture of 0.6 mL toluene, 2.4 mL n -heptane, and 80 mg sorbitan monooleate (Span-80). The resulting water-in-oil type emulsion was gradually injected into 25 mL of 1.5 mol L(-1) hydrochloric acid solution containing 30 mmol L(-1) 8-quinolinol and 1.0 mol L(-1) of ammonium sulfate and was dispersed as numerous tiny globules by stirring for 40 min. More than 90% of the iron(III) diffused through the oil layer to the external hydrochloric acid solution with the aid of complexation with 8-quinolinol, whereas trace heavy metals, e.g. Cr(III), Mn(II), Co(II), Ni(II), Cu(II), and Pb(II), remained quantitatively in the internal aqueous phase. After collecting the dispersed emulsion globules, they were demulsified and trace metals in the segregated aqueous phase were determined by graphite-furnace atomic absorption spectrometry. Owing to sufficient removal of the iron matrix trace metal impurities in high-purity iron were successfully determined without interference, as was confirmed by analysis of certified reference materials.

Sulfonylcalix[4]arenetetrasulfonate as pre-column chelating reagent for selective determination of aluminum(III), iron(III), and titanium(IV) by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection.

Sulfonylcalix[4]arenetetrasulfonate (SO(2)CAS) has been examined as a pre-column chelating reagent for ultratrace determination of metal ions by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection. Metal ions were converted into the SO(2)CAS chelates in an acetic buffer solution (pH 4.7). The chelates were injected onto a n-octadecylsilanized silica-type Chromolithtrade mark Performance RP-18e column and were eluted using a methanol (50wt.%)-water eluent (pH 5.6) containing tetra-n-butylammonium bromide (7.0mmolkg(-1)), acetate buffer (5.0mmolkg(-1)), and disodium ethylendiamine-N,N,N',N'-tetraacetate (0.10mmolkg(-1)). Under the conditions used, Al(III), Fe(III), and Ti(IV) were selectively detected among 21 kinds of metal ions [Al(III), Ba(II), Be(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hf(IV), In(III), Mg(II), Mn(II), Mo(VI), Ni(II), Pb(II), Ti(IV), V(V), Zn(II), and Zr(IV)]. The detection limits on a 3sigma blank basis were 8.8nmoldm(-3) (0.24ngcm(-3)) for Al(III), 7.6nmoldm(-3) (0.42ngcm(-3)) for Fe(III), and 17nmoldm(-3) (0.80ngcm(-3)) for Ti(IV). The practical applicability of the proposed method was checked using river and tap water samples.

Preconcentration of copper, cadmium, and lead with a thiacalix[4]arenetetrasulfonate-loaded Sephadex A-25 anion-exchanger for graphite-furnace atomic-absorption spectrometry.

A rapid column-adsorption method has been developed for concentrating traces of copper, cadmium, and lead in water prior to their determinations by graphite-furnace atomic-absorption spectrometry. The adsorbent used was prepared by loading a strongly basic anion-exchanger QAE-Sephadex A-25 (50 mg) with thiacalix[4]arenetetrasulfonate (20 micromol). Two-hundredfold preconcentration of the analyte elements was achieved by passing 100 mL of sample solution (pH 8.0) through a column packed with the adsorbent (6 mm i.d. x 7 mm high) at a flow rate of 10 mL min(-1) and by the subsequent elution with 500 microL of aqueous nitric acid solution (1 mol L(-1)). The practical applicability of the proposed method was evaluated by analyzing certified reference seawater samples.