Strategy for water analysis using ICP-MS

The developed strategy permits determination in three steps of sixty-seven elements using inductively coupled plasma mass spectrometry (ICP-MS). Sodium, Mg, Si, S, Cl, K, and Ca are determined in a first step; B, Al, P, Cr, Fe, Mn, Ni, Cu, Zn, As, Se, Ag, Cd, Sb, Ba, Hg, and Pb are determined in a second step; and Li, Be, Ti, V, Co, Ga, Ge, Br, Rb, Sr, Y, Zr, Nb, Mo, Sn, Te, I, Cs, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Pt, Au, Tl, Bi, Th, and U are analyzed in a third step. The figures of merit obtained are adequate to carry out water quality monitoring and other hydrochemical studies, such those based in the application of hydrochemical fingerprinting to water management.     

Interactive effects of age and gender on levels of toxic and potentially toxic metals in children hair in different urban environments

Children growth and development may be affected by metal exposure. The objective of the present study was to investigate the interactive effects of age and gender on children hair toxic metal levels in urban environment of two Russian cities. A total of 2021 children living in Moscow and Novosibirsk aged 1–18 years old were examined. Hair Al, As, Cd, Hg, Ni, Pb and Sn levels were assessed using inductively-coupled plasma mass-spectrometry in dynamic reaction cell mode. Children from Novosibirsk were characterised by higher hair Al (37%), As (385%), Cd (127%), Hg (11%), Ni (23%), Pb (72%) and Sn (25%) in comparison to Moscow values. In the general cohort, boys had higher Al (13%), As (51%), Cd (65%), Pb (63%) and Sn (18%) levels, whereas hair Ni was higher in girls (17%). Further analysis demonstrated age-specific gender differences. In particular, only hair Ni and Cd levels were higher in male toddlers and pre-schoolers from Novosibirsk as compared to females. No gender difference was detected in Moscow. Maximal gender differences in hair metal levels were detected in adolescents for both locations. International Union of Pure and Applied Chemistry (IUPAC) reference values for all groups were also calculated. The overall reference limits for the studied children population were Al (1.335–3.340 µg/g), As (0.021–0.384 µg/g), Cd (0.000–1.389 µg/g), Hg (0.024–0.722 µg/g), Ni (0.076–0.701 µg/g), Pb (0.050–1.490 µg/g) and Sn (0.070–1.026 µg/g). Two-way ANOVA demonstrated significant effects of age, gender and age*gender interaction on hair metals in both cities. At the same time, the age-specific changes in hair metal content were more expressed in children from Novosibirsk, being exposed to higher metal pollution. The obtained data demonstrate that age, gender as well as the particular rate of pollution in each location should be taken into account during interpretation of hair test results.     

Multielemental analysis of ferromanganese nodules from Central Indian Ocean Basin by PIXE

Ferromanganese nodules found on the Ocean bed are complex heterogenous mixtures of several components. Two nodules from Central Indian Ocean Basin (CIOB) were analysed by proton induced X-ray emission (PIXE) technique using 3UD Tandem pelletron. The precision and the accuracy of this technique for chemical analyses has been confimed by analysing USGS Geological Standards. Thick sample targets were bombarded by 3 MeV protons for the multielemental analysis. GUPIX-96 software was used for spectral data analysis. Quantative estimate of K, Ca, Tl, V, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Mo, Ba, Ce, Tl and Pb has been ascertained. The occurrence of Ga, Ge, Rb and Zr in nodules from this region is reported for the first time. The role of manganese and iron oxide phases in determining the uptake of various trace elements from ocean water and bottom sediment pore water has been discussed.     

The application of discontinuous,countercurrent, liquid-liquid extraction to the study of the distribution of metal ions between hydrochloric acid and methyl isobutyl ketone

Summary The extraction of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi from hydrochloric acid into methyl isobutyl ketone has been studied as a function of hydrochloric acid concentration. The results are presented in graphical form. The data were obtained by studying the distribution patterns of the elements after equilibration on a Craig countercurrent liquid-liquid extraction apparatus.

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Zusammenfassung Die Extraktion der Elemente Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb und Bi mit Methylisobutylketon aus salzsaurer Lösung als Funktion der Säurekonzentration wurde studiert. Die Ergebnisse wurden aus den Spitzen der Verteilungskurven nach Einstellung des Gleichgewichts in einem diskontinuierlichen Gegenstrom-flüssig-flüssig-Extraktionsapparat berechnet.

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Résumé On a étudié l'extraction des éléments Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb et Bi en solution chlorhydrique par la méthylisobutylcétone. On présente les résultats sous forme graphique. Les données ont été obtenues en étudiant les diagrammes de distribution des éléments après équilibrage sur un appareil Craig à extraction à contre-courant liquide-liquide.

     

Systematic study of the solvent extraction of metal oxinates

The extraction of 32 metals (Be, Mg, Ca, Sr, Ba, Sc, La, Ti, Zr, Th, V, Nb, Cr, Mo, W, U, Mn, Fe, Co, Ni, Pd, Cu, Ag, Zn, Cd, Hg, Al, Ga, In, Tl, Pb and Bi) with oxine solution has been studied. The effects of pH, oxine concentration and water-soluble complexing agents (oxalic acid, tartaric acid, hydrocyanic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid and 1,2-diaminocyclohexanetetraacetic acid) have been investigated. From these results the extraction constants and stability constants ot the metal complexes with the various complexing agents investigated have been calculated.     

Determinations de traces dans les semi-conducteurs par activation neutronique

Résumé On décrit la détermination de traces dans le germanium, le silicium et le sélénium. En appliquant des techniques gamma spectrométriques, précédées ou non de séparations chimiques il est possible de doser les éléments suivants dans (1) germanium: As, Cu, Au, Ga, Zn, Hg, Cr, Sn, Sb, Co, In, Ni, Ir, Se, Sc, Ag, Ta, Hf et U; (2) silicium: P, Au, Sb, Ga, Fe, K, Cr, Mo, Sn, As, Co, In, Zn, Cu, W, Ta, Na, Eu, Sm, La, Sc et T1; (3) sélénium: Cl, Br, I, P, S, Te, Na, K, Cr, Fe, Co, Cu, Zn, Ga, Sc, Ag, Cd, La, W, Au et Tl. Les concentrations et ou limites de détections varient de quelques parties par million à 10⁻³ parties par milliard.     

Elemental content in wheat products of Al-Qusim region, Saudi Arabia using the INAA technique

Wheat is one of the most grown crops in Saudi Arabia. It is grown in various regions of the country. Accurate knowledge of the elemental concentrations in wheat and its products (bran and flour) is of great importance from a nutritional point of view. Wheat samples were obtained from the Al-Qusim region, 300 km northwest of Riyadh, and analyzed. Up to 50 elements (Al, Sb, As, Ba, Br, Cd, Ca, Cs, Cl, Cr, Co, Cu, Ga, Au, Hf, In, I, Ir, Fe, Mg, Mn, Hg, Mo, Ni, K, Rb, Sc, Se, Ag, Na, Sr, Ta, Te, Th, Sn, Ti, W, U, V, Zn, Zr, Ce, Dy, Eu, La, Lu, Nd, Sm, Tb and Yb) were determined in the wheat products. It was observed that the elemental content of bran was much higher than that of white flour.     

Selective separation of indium from zinc, lead, gallium and many other elements by cation-exchange chromatography in hydrohalic acid-acetone medium

Indium can be separated from Zn, Pb(II), Ga, Ca, Be, Mg, Ti(IV), Mn(II), Fe(III), Al, U(VI), Na, Ni(II) and Co(II) by selective elution with 0.50M hydrochloric acid in 30% aqueous acetone from a column of AG50W-X8 cation-exchange resin, all the other elements being retained by the column. Lithium is included in the elements retained by the column when 0.35M hydrochloric acid in 45% aqueous acetone is used for eluting indium, but the elution of indium is slightly retarded. Ba, Sr, Zr, Hf, Th, Sc, Y, La and the lanthanides, Rb and Cs should also be retained according to their distribution coefficients. Cd, Bi(III), Au(III), Pt(IV), Pd(II), Rh(III), Mo(VI) and W(VI) can be eluted with 0.20M hydrobromic acid in 50% aqueous acetone before the elution of indium, and Ir(III), Ir(IV), As(III), As(V), Se(IV), Tl(III), Hg(II), Ge(IV), Sb(III) and Sb(V), though not investigated in detail, should accompany these elements. Relevant distribution coefficients and elution curves and results for analyses of synthetic mixtures of indium with other elements are presented.     

Investigations on the development of a scheme of silicate analysis based principally on spectrographic and ion exchange techniques

An attempt is made to integrate into an analytical “scheme” a series of investigations on the complete analysis of the naturally occurring silicates. Emphasis is placed on simplicity, high sensitivity (if necessary), wide element coverage, speed and satisfactory accuracy, The analytical operations involve ion exchange, solvent extraction and spectrochemical techniques. Observations are made on the following elements: Ag, Al, Au, Ba, Bi, Ca, Cd, Ce, Cs, Cu, Fe, Ga, In, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pd plus other elements of the platinum group, Rh, Sc, Si, Sn, Si, Ti, Tl, V, Y, Zn and Zr.     

Extraction into methyl isobutyl ketone of metal complexes with ammonium pyrrolidine dithiocarbamate formed in strongly acidic media

It is shown that stable metal complexes with ammonium pyrrolidine dithiocarbamate (APDC) are formed in strongly acidic (0.5–6 M) solutions and can be extracted into methyl isobutyl ketone (MIBK), although APDC is normally used for extractions from solutions at pH 2–12. Percentage extraction curves are presented for 24 elements (Ag, As, Au, Bi, Cd, Co, Cu, Fe, Ga, Ge, Hg, In, It, Ni, Os, Pb, Pd, Pt, Rh, Ru, Sb, Sn, Tl and Zn) from solutions of hydrochloric or nitric acid with and without addition of APDC. Some elements (e.g., Fe, Ga, Ge, In and Au) show identical extractions as their chloro complexes in hydrochloric acid with or without APDC. Others (e.g., Ni, Cu, Pd, As, Ag, Sb, It, Hg and Bi) are strongly extracted (K_d ? 20), from 2 M hydrochloric or nitric acid in the presence of APDC. Palladium (K_d = 8000), Sb (K_d = 10 000), and Bi (K_d = 3500) are particularly easily extracted. The potential of the extraction system was tested by extraction and quantification of palladium from the CANMET standard ore PTC-1; the mean value found was 12.55 μg g^?1 (ppm) palladium with a relative standard deviation of 7.6% (n = 12) and a relative error of 1.2% from the recommended value of 12.70 μg g^?1.     

Ion flotation behaviour of thirty-one metal ions in mixed hydrochloric/nitric acid solutions

The ion flotation of 31 metal ions in hydrochloric/nitric acid solution with the cationic surfactant cetylpyridinium chloride was investigated. A 25-ml portion of 0.27-2.87 x 10(-4)M metal ion and 1.8-6.0 x 10(-4)M cetylpyridinium chloride solution in 0.17-3.4M acid mixture ([HCl]:[HNO(3)] = 2.4:1) was subjected to flotation in a cell, 22.5 cm high and 4.0 cm in diameter, for 5 min, with nitrogen bubbles. Ir(IV), Pt(IV), Ge(IV), Sn(IV), Bi(III), Au(III), Tl(III), Pd(II) and Sn(II) were floated from solution in 95-100% yield; Ru(III), Rh(III), Ir(III), Hg(II), Ag(I) and Tl(I) were partly floated, while Cr(VI), Ti(IV), Zr(IV), Ga(III), In(III), Fe(III), Sb(III), Al(III), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), CD(II) and Pb(II) were floated with less than 20% yield. The flotation behaviour of these metal ions in the mixed acid system was compared with that in hydrochloric acid. The flotation is more efficient in the mixed acid system.     

“Multitracer” a new tracer technique — Its principle,features, and application

We established Multitracer, a new versatile radiotracer technique, for simultaneous tracing of a number of elements in various chemical, environmental, and biological systems. Metal foil targets (typically Au, Ag, Ge, Cu and Fe) are irradiated with C, N, or O ions accelerated up to 135 MeV/nucleon by RIKEN Ring Cyclotron. Radiochemical procedures have been developed to remove the target material leaving the nuclides as Multitracer solutions containing various radionuclides of Be, Na, Mg, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Te, I, Ba, Ce, Pm, Eu, Gd, Tb, Tm, Yb, Lu, Hf, W, Re, Os, Ir, Pt, and Hg. Multitracers enable efficient tracing of a number of elements, and comparison of their behavior under strictly identical experimental conditions. Such features will be demonstrated by means of an example of application to a model experiment for the study of removal mechanism of various elements from the ocean.     

Study of hair element content from an urban Bulgarian population using NAA assessment of environmental status

In this preliminary study, scalp hair samples from 36 individuals resident in Sofia, Bulgaria, were analysed and Ag, Al, As, Au, Ba, Br, Ca, Cd, Ce, Cl, Co, Cr, Cs, Cu, F, Fe, Hg, I, K, La, Mg, Mn, Mo, Na, Ni, Rb, S, Sb, Sc, Se, Sn, Sr, Ti, V, W, and Zn were determined. Instrumental neutron activation analysis (INAA) methods were used. Three washing procedures.: distilled-deionised water; acidacetone-water; and Triton X-100 detergent-water, showed a variable elemental change strongly dependent on the procedure used. More than 18 elements (Al, As, Ba, Ca, Ce, Cl, Co, Cs, F, Fe, I, K, La, Mo, Na, Ni, Sb, Sc, Sr and V) were easily removed by water-washing. Triton X-100 detergent was more effective in removing Ag, As, Au, Cl, Cs, K, Na and Rb; but not Hg. Only S and Zn were strongly incorporated in the hair structure (less than 10% being removable by any washing technique). There is no significant age correlation with any element between the various hair treatment groups. Elevated cadmium levels were found in the hair of smokers (0.711–4.913 g/g Cd) compared with nonsmokers (0.568–2.681 g/g Cd). Comparison of the elemental data for distilled water-washed hair and studies from Oxford, England and Hastings, and Hastings, New Zealand (using the same INAA method) revealed interesting variations dependent on local industrial and nutritional factors.     

Multielement standards in routine reactor neutron activation analysis

The application of multielement standards (MES) in routine neutron activation analysis brings a whole range of advantages. This paper deals with the experience obtained during many years of application of these MES. Nine of these MES contain a total of 50 elements in suitable combinations and concentrations; thus, the determination of most of the common elements by NAA can be carried out simultaneously. This refers to the following elements: Na, Mg, Al, Cl, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Ag, Cd, In, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, W, Re, Au, Hg, Th and U. For the determination of the remaining elements such as Zr, Ta, Ir etc., single element standards (SES) are used.     

Traceability along the production chain of Italian tomato products on the basis of stable isotopes and mineral composition

The paper shows the variability of stable isotope ratios and mineral composition in tomato and derivatives along the production chain (juice, passata and paste) in order to evaluate the possibility of tracing their geographical origin. The ratios (13)C/(12)C, (15)N/(14)N, (18)O/(16)O, D/H, (34)S/(32)S and the content of Li, Be, B, Na, Mg, Al, P, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Ag, Cd, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Tm, Yb, Ir, Tl, Pb, U and of nitrates, chlorides, sulphates and phosphates were measured by Isotope Ratio Mass Spectrometry, Inductively Coupled Plasma Mass Spectrometry and Ion Chromatography, respectively. The tomato products were from three Italian regions - Piedmont, Emilia Romagna, and Apulia. By applying linear discriminant analysis on 17 of these parameters (Gd, La, Tl, Eu, Cs, Ni, Cr, Co, δ(34)S, δ(15)N, Cd, K, Mg, δ(13)C, Mo, Rb and U) excellent discrimination among products from the three regions was achieved. Irrespective of the processing technology, over 95% of the samples were correctly reclassified in cross-validation into the production site. The use of these parameters will allow the development of analytical control procedures that can be used to check the geographical provenance of Italian tomatoes and products derived from them.     

Characterization of deep sea sediments by INAA for radioactive waste management purposes

An instrumental neutron activation analysis method, using both reactor flux and epi-cadmium neutrons, has been developed for the determination of major, minor and trace elements in sub-seabed sediments. The method involves two different irradiations followed by three different counting periods using high-resolution Ge(Li) and low-energy photon detectors. The list of elements determined includes Ag, Al, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Dy, Eu, Fe, Ga, Gd, Hf, Hg, I, In, K, La, Lu, Mg, Mn, Mo, Na, Nd, Ni, Pt, Rb, Re, Rh, Sb, Sc, Se, Si, Sm, Sn, Sr, Ta, Tb, Th, Ti, Tm, U, V. W, Yb, Zn, and Zr. The accuracy of the method has been evaluated by analyzing four different standard reference materials. The method has been applied to core samples collected from the Great Meteor East and the South Nares Abyssal Plain which are being evaluated as potential sites for the possible disposal of vitrified highly active waste.     

Trace element content of some Polish hard and brown coals

Instrumental neutron activation analysis /INAA/ method was applied to measure major, minor and trace elements in 34 samples of hard and brown coal originating from eight Polish coal mines. The elemental concentrations of 38 elements /Na, Mg, Al, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Br, Rb, Sr, Mo, Ag, Cd, In, Sb, I, Cs, Ba, La, Ce, Sm, Eu, Lu, W, Au and Th/ are presented and compared with published data for coals from various origin. Enrichment factors, calculated relative to iron and the average crustal rock composition, indicated that several elements are highly enriched in Polish coals.     

Use of INAA and ICP-MS for the assessment of trace element mass fractions in adult and geriatric prostate

The variation with age of the mass fraction of 54 trace elements (Ag, Al, As, Au, B, Be, Bi, Br, Cd, Ce, Co, Cr, Cs, Dy, Er, Eu, Fe, Ga, Gd, Hf, Hg, Ho, Ir, La, Li, Lu, Mn, Mo, Nb, Nd, Ni, Pb, Pd, Pr, Pt, Rb, Re, Sb, Sc, Se, Sm, Sn, Ta, Tb, Te, Th, Ti, Tl, Tm, U, Y, Yb, Zn, and Zr) in intact nonhyperplastic prostate of 65 healthy 21–87 year old males was investigated by instrumental neutron activation analysis with high resolution spectrometry of long-lived radionuclides and inductively coupled plasma mass spectrometry. This work revealed that there is a significant tendency for an increase in Bi, Cd, Co, Fe, Hg, Sc, Sn, Th, U, and Zn (p < 0.0014) mass fraction in normal prostate from age 21 years to the sixth decade. In the sixth to ninth decades the mass fractions of almost all chemical elements investigated in nonhyperplastic prostates were maintained at approximately stable levels. Our finding of correlation between pairs of prostatic chemical element mass fractions indicates that there is a great disturbance of prostatic chemical element relationships with increasing age.     

Crystallographic and structural characterisation of heterometallic platinum compounds: Part I. Heterobinuclear Pt compounds

This review covers almost 290 heterobinuclear Pt derivatives. When the heterometals (M) are non transition and the binuclear are found both with and without a metal to metal bond. Where M is a transition metal or actinide, only those with a metal-metal bond have been included here. There are thirteen non-transition metals (Sn, Hg, Ge, Sb, Tl, Zn, Pb, Cd, Na, K, Ga, Ca and In). The shortest Pt-M bond distance is 235.2(1) (Pt-Ge). There are eighteen transition metals (Fe, W, Rh, Re, Pd, Ag, Ir, Mo, Mn, Re, Co, Cu, Cr, Au, Ni, Ti, Ta and V). The shortest Pt-M bond distance is 249.5(2) pm (Pt-Cr). There is one example of an actinide, Pt-Th at 298.4(1) pm. The Pt atom has oxidation numbers 0, +2 and +4. The Pt coordination geometries include square planar (most common), trigonal bipyramidal, pseudo octahedral (Pt(IV)) and a few prevalently capped trigonal prismatic seven coordinate species. There are at least two types of isomerism distortion and polymerisation. Factors affecting bond lengths and angles are discussed and some ambiguities in coordination polyhedra are outlined.      

Selective and quantitative separation of zinc and lead from other elements by cation-exchange chromatography in hydrohalic acid-acetone solutions

Zinc and lead can be separated from Cd, Bi(III), In and V(V) by eluting these elements with 0.2M hydrochloric acid in 60% acetone from a column of AG50W-X8 cation-exchange resin, zinc and lead being retained. Mercury(II), Tl(III), As(III), Au(III), Sn(IV), Mo(VI), W(VI) and the platinum metals have not been investigated quantitatively, but from their distribution coefficients, should also be eluted. Vanadium(V), Mo(VI) and W(VI) require the presence of hydrogen peroxide. Zinc and lead can be eluted with 0.5M hydrochloric acid in 60% acetone or 0.5M hydrobromic acid in 65% acetone and determined by AAS; the alkali and alkaline-earth metal ions, Mn(II), Co, Ni, Cu(II), Fe(III), Al, Ga, Cr(III), Ti(IV), Zr, Hf, Th, Sc, Y, La and the lanthanides are retained on the column, except for a small fraction of copper eluted with zinc and lead. Separations are sharp and quantitative. The method has successfully been applied to determination of zinc and lead in three silicate rocks and a sediment.