Anreicherung und spektrochemische Bestimmung von Spurenelementen in reinsten Thalliumpr?paraten

Zusammenfassung Zur Anreicherung von Spurenelementen aus Lösungen reinster Thalliumpräparate wird die Matrix Thallium als TlJ ausgefällt. Dabei bleiben die Spuren Mg, Zn, Al, Ga, In, Fe, Co, Ni, Mn, Sn, La, Ce, Th und U quantitativ in Lösung, während Bi, Cu, Pb und Cd sowie die Edelmetalle Ag, Hg, Pd, Au und Pt vom Niederschlag mitgerissen werden. Die Adsorption der für die Reinheitsprüfung des Thalliums wichtigen Elemente Bi, Cu, Pb und Cd kann verhindert werden, wenn sie mit Hilfe von ÄDTA in Komplexanionen übergeführt werden. Als Fällungsmittel wird NaJ verwendet. Zur spektrochemischen Bestimmung werden Pb, Cd, Bi, Ni, Co und In als DDTC-Komplexe mit Chloroform extrahiert. Nach Zusatz einer Mischung von Lithiumcarbonat-Kohle und den Referenzelementen Sn und Pd wird der Eindampfrückstand im Gleichstrombogen analysiert. Cu und Fe werden photometrisch bestimmt.

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Enrichment and spectrochemical determination of trace elements in high-purity thallium preparations

For the enrichment of trace elements in solutions of high-purity thallium samples, thallium is precipitated in form of TlI. In this process the noble metals Ag, Hg, Pd, Au, Pt and also Bi, Cu, Pb and Cd will be co-precipitated, whereas many other elements (Mg, Zn, Al, Ga, In, Fe, Co, Ni, Mn, Sn, La, Ce, Th, U) will remain completely in solution. The adsorption of the four elements Bi, Cu, Pb, Cd, which are important for the purity control of thallium compounds, can be prevented, if they are complexed with EDTA to form complex anions. The precipitating reagent is NaI. For the spectrochemical determination of Pb, Cd, Bi, Ni, Co, and In, the trace elements are extracted as DDTC complexes with chloroform. After the addition of a mixture of Li₂CO₃, carbon, and the reference elements Sn and Pd, the sample is analysed, using the d.c. arc. Cu and Fe are determined spectrophotometrically.

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Wir danken dem Fonds der chemischen Industrie für die finanzielle Unterstützung dieser Arbeit.     

A pilot study for the production of a certified reference material for trace elements in honey

In the context of the general mandate of the European Union Community Reference Laboratory (CRL) for residues in living animals and their products established at the Istituto Superiore di Sanità, a pilot study was undertaken to assess the possibility of producing a new certified reference material (CRM) for trace elements in a matrix of honey. The elements considered were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V and Zn. Their determination was performed by inductively coupled plasma (ICP)-based techniques. Data obtained with different ICP techniques were generally in good agreement. In light of these results, the next step was the effective production of a candidate CRM in a honey matrix. In the preliminary phase, two different types of honey, i.e., Eucalyptus (solid and sticky) and Robinia (viscous and sticky), were pretreated at the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (EC-JRC-IRMM) in order to produce the materials candidate for the certification process. Approximately 600 ampoules were thus produced for the Robinia honey and 450 ampoules for the Eucalyptus honey, each ampoule containing 5 g of an aqueous solution of honey (with 20% and 30% high purity water, respectively) and sealed under inert gas (Ar). A ring test to determine the levels of the chemical elements and a long-term study to evaluate the stability of the samples is in progress. Tentative figures for the analytes of interest are (in ng g⁻¹): Robinia, As, 1.28±0.09; Cd, 0.59±0.08; Cr, 2.36±0.21; Cu, 57.6±3.2; Fe, 209±9; Mn, 90.8±3; Ni, 18.1±0.6; Pb, 23±1.5; Sn, 8.10±0.35; V, 1.19±0.37; and Zn, 178±4; Eucalyptus, As, 3.18±0.21; Cd, 0.70±0.08; Cr, 2.73±0.22; Cu, 141±6; Fe, 926±16; Mn, 1905±81; Ni, 7.77±0.4; Pb, 138±4; Sn, 7.97±0.16; V, 3.47±0.15; and Zn, 405±9.     

Grundlagen zur halbquantitativen Bestimmung von zwanzig Elementen in der Lasermikrospektralanalyse

Zusammenfassung Für die folgenden 20 Elemente wurden die Grundlagen für eine halbquantitative Konzentrationsbestimmung mit Hilfe des Laser-Mikrospektralanalysators ermittelt, und zwar differenziert für Untersuchungen an oxidischen und an metallischen Materialien: Mg, Al, Si, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pb, Bi, Fe bzw. Au.

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Principles of semi-quantitative determination of 20 elements by laser-microspectroscopy

The principles for the determination of the following 20 elements by Laser-microspectroscopy have been investigated separately for oxidic and metallic materials: Mg, Al, Si, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, Pd, Ag, Cd, In, Sn, Sb, Pb, Bi, Fe resp. Au.

     

Sediment Assessment of the Pchelina Reservoir,Bulgaria

The temporal dynamics of anthropogenic impacts on the Pchelina Reservoir is assessed based on chemical element analysis of three sediment cores at a depth of about 100–130 cm below the surface water. The ¹³⁷Cs activity is measured to identify the layers corresponding to the 1986 Chernobyl accident. The obtained dating of sediment cores gives an average sedimentation rate of 0.44 cm/year in the Pchelina Reservoir. The elements’ depth profiles (Ti, Mn, Fe, Zn, Cr, Ni, Cu, Mo, Sn, Sb, Pb, Co, Cd, Ce, Tl, Bi, Gd, La, Th and U_nat) outline the Struma River as the main anthropogenic source for Pchelina Reservoir sediments. The principal component analysis reveals two groups of chemical elements connected with the anthropogenic impacts. The first group of chemical elements (Mn, Fe, Cr, Ni, Cu, Mo, Sn, Sb and Co) has increasing time trends in the Struma sediment core and no trend or decreasing ones at the Pchelina sampling core. The behavior of these elements is determined by the change of the profile of the industry in the Pernik town during the 1990s. The second group of elements (Zn, Pb, Cd, Bi and U_nat) has increasing time trends in Struma and Pchelina sediment cores. The increased concentrations of these elements during the whole investigated period have led to moderate enrichments for Pb and U_nat, and significant enrichments for Zn and Cd at the Pchelina sampling site. The moderately contaminated, according to the geoaccumulation indexes, Pchelina Reservoir surface sediment samples have low ecotoxicity.     

Estimation of Uncertainty Budgets in Analysis of Nickel by ICP-MS and High-Resolution Mass Spectrometry with a Glow Discharge

Moscow University Chemistry Bulletin - This paper estimates uncertainty budgets in determining the content of impurities of 15 elements (P, Mn, Fe, Cu, Zn, As, Se, Ag, Cd, Sn, Sb, Te, Tl, Pb, Bi)...     

Spectrophotometric determination of La, Ce, Pr and Nd in the presence of copper by use of arsenazo III

Summary Arsenazo III was applied to the determination of the total amount of La, Ce, Pr and Nd in the presence of Cu, using sodium thiosulphate for masking Cu up to 50 mg. The lanthanides can be analyzed within the range of 0–2.4 or in presence of Pb, Al, Ni, Fe 0–1.6 mg/l. Interferences of Zn, Mn, Ni, Al, Sn, Pb and Fe were examined. The procedure was applied to the determination of Ce in CuSnCe alloys and Al and Pb brasses without prior separation of the matrix.     

Diagrammes potentiel—niveau d'acidite dans les milieux H2OH3PO4—I Systemes electrochimiques ne faisant pas intervenir le proton

The conditional potentials of redox systems not involving protons have been studied as a function of phosphoric acid concentration (1–14M), with the ferricinium/ferrocene couple as the comparison system. The following systems were considered: Cu(II)/Cu, Cd(II)/Cd, Sn(II)/Sn, Zn(II)/Zn, Ag(I)/Ag, Pb(II)/Pb, Hg(II)/Hg, Bi(III)/Bi and particularly Fe(III)/Fe(II) and Fe(II)/Fe. The hexacyanoferrate(III)/hexacyanoferrate(II) and iodine/iodide couples were also studied. The results are presented as a potential—H₃PO₄ concentration diagram (or potential—acidity level diagram).     

Determination of copper, iron, manganese and zinc in river and estuarine water by atom trapping-flame atomic absorption spectrometry

Summary A simple method is described for the atomic absorption (AA) determination of Cu, Fe, Mn and Zn in river and estuarine water using two atom trapping techniques: a water-cooled dual silica tube and a commercially available double-slotted quartz tube mounted in an air-acetylene flame. Rapid, accurate analyses can be achieved using continuous aspiration. The concentration detection limits were 0.9, 1.5 and 0.3 ng ml^–1 for Cu, Mn and Zn, respectively, using a 2 min in situ preconcentration time with the dual silica tube atom trap and 4.0, 12.1, 2.0 and 1.2 ng ml^–1 for Cu, Fe, Mn and Zn, respectively, using the double-slotted quartz tube. The relative standard deviations are of the order of 2.9–6.9% for both techniques. The accuracy was assessed by analyses of NRCC SLRS-2 riverine and SLEW-1 estuarine water reference materials. Basic performance characteristics are also given for Ag, Bi, Cd, In, Pb and Tl using the dual silica tube atom trap.     

Emission-spectrometric determination of trace non-rare earth elements in yttrium oxide using AgF-Ga2O3 mixed carrier

Summary An emission-spectrometric method is described for the quantitative determination of traces of non-rare earth elements in yttrium oxide, employing addition of AgF-Ga₂O₃ mixed carrier. This addition effects an increase of the rate of evaporation of the analytical elements and of the number of atoms in the arc plasma. It enhances the sensitivity of the analytical elements to a larger extent than other carriers and permits the determination of microquantities of the elements (Mg, Ca, Mn, Co, Fe, Pb, Cu, Cd, Al, B, Sn, As, Bi) within limits of detection from 0.1 to 13 ppm in high-purity yttrium oxide. The coefficients of variation are less than 20%.

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Emissionsspektrometrische Bestimmung von nicht zu den Seltenen Erden gehörenden Elementspuren in Yttriumoxid mit Hilfe eines AgF-Ga₂O₃ -Trägergemisches

Zusammenfassung Das Trägergemisch bewirkt eine Erhöhung der Verdampfungsgeschwindigkeit der zu bestimmenden Elemente und der Anzahl der Atome im Bogenplasma. Es verbessert mehr als andere Träger die Empfindlichkeit und ermöglicht die Bestimmung von Mikromengen der Elemente (Mg, Ca, Mn, Co, Fe, Pb, Cu, Cd, Al, B, Sn, As, Bi) in hochreinem Yttriumoxid mit Nachweisgrenzen von 0,1–13 ppm. Die Variationskoeffizienten liegen unter 20%.

     

Analysis of Impurities in Mixtures of West-Siberian Crude Oils

The content of B, Mg, Na, Al, P, V, Mn, Cu, Cr, Fe, Ni, Zn, Ag, Br, Sn, I, Ba, W, Pb, and Bi in 24 samples of industrial mixtures of West-Siberian oils was studied using the method of inductively coupled plasma with mass spectrometric registration.     

Chelate von β-dicarbonylverbindungen und ihren derivaten: Teil XXXVI. Die extraktionsphotometrische bestimmung von cadmium mit thiodibenzoylmethan im vergleich mit anderen spezialreagenzien

Thiodibenzoylmethane is a suitable reagent for the extraction and photometric determination of traces of cadmium. There is no interference from 10000-fold amounts of alkaline and alkaline earth metals, B, Al, Ga, In, Mn, Fe, Cr, and from 1000-fold amounts of As, Sb, Sn, Pb, Bi, Cu, Co, Ni, Pd; Ag, Hg, Tl and Zn are tolerated up to a 100-fold excess. The proposed method is compared with various other possibilities for cadmium determinations.     

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.

     

Human hair as a marker of pollution by chemical elements emitted by a thermoelectric power plant

A preliminary study was undertaken to assess the risk posed to the environment and health of residents by trace elements released by fuel combustion in the thermoelectric power plant of Pian de’ Gangani (Montalto di Castro, Latium, Italy). In this context, analysis of human hair can be considered as an advantageous approach to monitor the exposure of population to the adverse effects of the power plant, which is now fully operative. To this purpose 92 healthy children (aged 9–10 years) were selected from two primary schools of Montalto di Castro and Pescia Romana. The young age of the donors guarantees that the effects of cosmetic treatment and occupational exposure on the representativeness of data are minimized. Hair samples were collected, washed and digested as prescribed by already well-established procedures. Inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were employed for the determination of the trace and minor elements of interest (As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sb, Se, Tl, V and Zn). The entire analytical procedure was checked for both measurement precision and accuracy by using the Certified Reference Material BCR No. 397 Human Hair. The mean values obtained were (in μg g⁻¹): As, 0.159±0.044; Ca, 393±187; Cd, 0.047±0.055; Co, 0.040±0.038; Cr, 0.704±0.208; Cu, 12.0±10.3; Fe, 12.1±10.8; Mg, 40.6±27.7; Mn, 0.383±0.296; Ni, 0.868±1.331; P, 141±138; Pb, 1.64±1.63; Sb, 0.041±0.058; Se, 0.430±0.135; Tl, 0.001±0.001; V, 0.185±0.158; and Zn, 177±173. These experimental figures can be assumed to be the baseline values prior to the full operation of the power plant. Within the next 4–5 years it is planned to conduct a similar study with a new group of subjects, comparable for age, sex, style of life and exposure mode, to the present ones so as to detect possible trends in the bioaccumulation of the above elements.     

Solvent extraction of metal xanthates

The solvent extraction of metal xanthates is reviewed with emphasis on the characteristics and analytical uses of ethyl xanthate complexes. Elements reviewed include As, Sb, Bi, Cd, Co, Cu. Cr, Ga, Au, In, Fe, Pb, Mn, Hg, Mo, Ni, Pd, Pt, Re, Ag, Se, Te, Tc, Tl, Sn, U, V and Zn.     

A comparison of an optimised sequential extraction procedure and dilute acid leaching of elements in anoxic sediments, including the effects of oxidation on sediment metal partitioning

The effect of oxidation of anoxic sediment upon the extraction of 13 elements (Cd, Sn, Sb, Pb, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As) using the optimised Community Bureau of Reference of the European Commission (BCR) sequential extraction procedure and a dilute acid partial extraction procedure (4 h, 1 mol L⁻¹ HCl) was investigated. Elements commonly associated with the sulfidic phase, Cd, Cu, Pb, Zn and Fe exhibited the most significant changes under the BCR sequential extraction procedure. Cd, Cu, Zn, and to a lesser extent Pb, were redistributed into the weak acid extractable fraction upon oxidation of the anoxic sediment and Fe was redistributed into the reducible fraction as expected, but an increase was also observed in the residual Fe. For the HCl partial extraction, sediments with moderate acid volatile sulfide (AVS) levels (1-100 μmol g⁻¹) showed no significant difference in element partitioning following oxidation, whilst sediments containing high AVS levels (>100 μmol g⁻¹) were significantly different with elevated concentrations of Cu and Sn noted in the partial extract following oxidation of the sediment. Comparison of the labile metals released using the BCR sequential extraction procedure (ΣSteps 1-3) to labile metals extracted using the dilute HCl partial extraction showed that no method was consistently more aggressive than the other, with the HCl partial extraction extracting more Sn and Sb from the anoxic sediment than the BCR procedure, whilst the BCR procedure extracted more Cr, Co, Cu and As than the HCl extraction.     

Kathodenstrahlpolarographische Bestimmung von Spurenelementen in Tetrachlorogolds?ure nach ionenaustausch-chromatographischer Trennung

Zusammenfassung Die kathodenstrahlpolarographische Bestimmung von Ni, Pb, Cu, Co, Fe, Mo, Te, Sn, Zn, Bi, Cd, Tl in Tetrachlorogoldsäure wird beschrieben. Die Nachweisgrenzen liegen im 10^–4%- bzw. 10^–5%-Bereich (Ni, Co, Mo). Die Spuren werden über einen Ionenaustauscher AG 1X8 untereinander und von der Matrix getrennt.

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Cathode-ray polarographic determination of trace elements in tetrachloroauric acid after separation by ion exchange

A method is described for the cathode-ray polarographic determination of traces of Ni, Pb, Cu, Co, Fe, Mo, Te, Sn, Zn, Bi, Cd, Tl in H(AuCl₄). Gold is separated from the trace metals by absorption on the strongly basic anion-exchange resin AG 1X8. The detection limits are within the ranges of 10^–4% and 10^–5% ((Ni, Co, Mo).

     

Spektrochemische Bestimmung von Spurenelementen in reinem Gold

Zusammenfassung Eine Spektrochemische Methode zur Bestimmung von Spuren der Elemente As, Sb, Fe, Mn, Pb, Ni, Bi, Cu, Pt, Pd, Cd, Rh und Ag in reinem Gold wird beschrieben. Zunächst wird das Gold durch Extraktion aus 3 N HCl mit Methylisobutylketon abgetrennt. Die Verunreinigungselemente werden dann an spektralreinem Graphitpulver mit 4% NaCl und 0,02% Co als Bezugselement adsorbiert und im Wechselstromabreißbogen 3,5 min bei 10 A angeregt. Die Spektren wurden mit einem UV-Spektrograph Q 24 auf ORWO-Spektralplatten Blau Extrahart aufgenommen. Die quantitative Bestimmungsgrenze für Mn, Pt und Ag beträgt 10^–6%, für Fe, Pb, Ni, Bi, Cu, Pd und Rh 10^–5% und für As, Sb und Cd 10^–4%. Die relative Standardabweichung überschreitet nicht 30%.

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Spectrochemical determination of trace elements in pure gold

A spectrochemical method for the determination of traces of As, Sb, Fe, Mn, Pb, Ni, Bi, Cu, Pt, Pd, Cd, Rh and Ag in pure gold is described. The gold is first separated by extraction into methyl isobutyl ketone from 3 N HCl solution and then the trace elements are adsorbed on spectrally pure carbon powder containing 4% NaCl and 0.02% Co as reference standard, and excited in an 10 A a.c. arc for 3.5 min. Emission spectra were recorded on ORWO-Blau Extrahart plates with an UV-spectrograph Q 24. Limits of detection were 10^–6% for Mn, Pt and Ag; 10^–5 % for Fe, Pb, Ni, Bi, Cu, Pd and Rh; 10^–4% for As, Sb and Cd. Relative standard deviation was not exceeding 30%.

     

高纯钛的辉光放电质谱法多元素分析

采用辉光放电质谱法(GD-MS)测定高纯钛中Mg、Al、Cr、Fe、V、Mn、Co、Ni、Cu、Zn、As、Sn、Sb、Ta、W、Pb、Bi等痕量杂质元素,并对GD-MS工作参数及条件进行了优化。主要元素与内标校正ICP-MS法定量分析的结果一致,对结果差异的原因进行分析,论述了Element GD辉光放电质谱仪在痕量杂质元素分析方面的优势。     

Cation-exchange separation and colorimetric determination of some elements in trace analysis of platinum-rhodium (10%) alloys

Summary A method of separation and colorimetric determination of trace amounts (10^–4–10^–5%) of Cu, Al, Fe, Bi, Pb, Mn, Cd, Zn, Co, and M in platinum-rhodium (10%) alloys has been developed. The elements to be determined are retained on a column containing the strongly acidic cation-exchanger Amberlite IR-120, from dilute hydrochloric acid medium (p_H 1–1.5), while platinum and rhodium pass through in the form of anionic chloride complexes. The individual metals are eluted and concentrated and then separated by extraction and carrier precipitation. The metals are determined by means of sensitive colorimetrie methods with dithizone (Cu, Bi, Pb, Cd, Zn), eriochromecyanine R (Al), 2-nitroso-1-naphthol (Co),-furildioxime (Ni), 1-(2-pyridylazo)-2-naphthol (Mn), and thiocyanate (Fe). The error of the determination does not exceed 15%.

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Zusammenfassung Eine Trennungs- und Bestimmungsmethode für Spuren (10^–4 bis 10^–5%) von Cu, Al, Fe, Bi, Pb, Mn, Cd, Zn, Co und Ni in PIatm-Rhodium-(10%)-Legierungen wurde ausgearbeitet.Die angeführten Elemente werden mit Amberlit IR-120 aus der verd. salzsauren Lösung (p_H 1 bis 1,5) von Platin und Rhodium getrennt, die als Anionchloridkomplexe im Eluat bleiben. Die einzelnen Metalle werden nach Elution aus ihrer Lösung durch Extraktion bzw. Mitfällung getrennt und kolorimetrisch mit Dithizon (Cu, Bi, Pb, Cd, Zn), Eriochromcyanin R (Al), 2-Nitroso-1-naphthol (Co),-Furildioxim (Ni), 1-(2-Pyridylazo)-2-naphthol (Mn) und Rhodanid (Fo) bestimmt. Der Fehler beträgt weniger als 15%,