Determination of platinum-group elements and rhenium in standard geological samples by isotope dilution with mass-spectrometric ending

A method is proposed for determining platinum-group elements, Ru, Pd, Os, Ir, Pt, and Re in geological samples by isotope dilution with mass spectrometric ending after sample decomposition with a mixture (1: 3) of conc. HCl + HNO₃ in a microwave system and the chromatographic separation of the analytes from the matrix on an AG 50W × 8 cation exchanger. The concentrations and isotope ratios are determined on high-resolution mass spectrometers ELEMENT and ELEMENT2. The attained detection limits range from 0.005 ng/g (Ir) to 0.2 ng/g (Pd) in solid samples. The use of isotope dilution improves the accuracy of determination and takes into account the matrix effect and changes in plasma parameters on the analytical signal. The method is tested in the analysis of standard samples of spinel lherzolite (GP-13) and serpentinite (UB-N). The relative standard deviation of the results of analysis is 5–22%, depending on the element and its concentration level (Ru, Pd, Re, Pt). In determining Os and Ir, a certain decrease in the accuracy and repeatability of the results is noticed.     

Simplified method for the determination of Ru, Pd, Re, Os, Ir and Pt in chromitites and other geological materials by isotope dilution ICP-MS and acid digestion

A method for the determination of low Ru, Pd, Re, Os, Ir and Pt abundances in geological reference materials by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion in a high pressure asher (HPA-S) is presented. The digestion technique is similar to that using Carius tubes but easier to handle and reaches higher temperatures. Osmium can be determined as OsO4 with ICP-MS directly after digestion through a sparging technique. The remaining elements are preconcentrated by means of anion column chromatography. The resin is digested directly without elution leading to high yields but this causes problems if Zr is present at higher levels in the silicate rich materials. The analytical results for international platinum group element (PGE) reference materials, chromitite CHR-Bkg, basalt TDB-1 and gabbro WGB-1, are presented and compared with literature data, demonstrating the validity of the described method. Although higher in concentration, PGEs determined for reference material WGB-1 were worse than for TDB-1 indicating a more inhomogeneous distribution of the platinum group mineral phases. The low PGE abundance chromitite standard, CHR-Bkg, is likely to be homogeneous for Ru, Re, Os and Ir and is recommended as a reference material for the study of chromitites. Detection limits (3s x total procedure blank) range from 0.012 ng (Re and Os) to 0.77 ng (Pt), which could be further improved by applying higher quality acids.     

Practical aspects of neutron activation determination of the platinum metals

Triple gamma coincidence counting of¹⁹²Ir allowed the determination of Ir by instrumental neutron activation analysis down to 1 ppb in ultrabasic rocks and down to ca. 20 ppb in some high-furnace slags; the limiting factor for the latter matrix was the presence of¹²⁴Sb. Radiochemical neutron activation analysis of the USGS standard rocks revealed that the Ir contents are up to three orders of magnitude lower than previously reported, except for the ultrabasic rocks. The factor of merit of several scintillation and semiconductor, gamma-ray detectors was determined for the neutron activation determination of Pd, Pt and Os. In the case of radiochemically pure sources, a NaI(Tl) wafer was preferred; in the presence of high-energy gamma-emitters, a Ge(Li) low-energy photon detector was superior.     

RECP calculations for reactions of H2 with Pt,Os, Ir,and Re — a systematic comparison

Summary Relativistic effective core potential calculations have been carried out for the reactions of Pt, Os, Ir, and Re with H₂. The calculations demonstrate the importance of a singly occupied 6s orbital for forming a strong bond. Pt and Ir have low-lying states with such occupancy, whereas Os and Re only attains this through a rather costly excitation. In consequence, the reaction barriers are considerably smaller for Pt and Ir than for Os and Re.     

New synthetic routes to cationic arene π-complexes of transition metals

A review is given of the authors' studies on the development of new methods for the synthesis of cationic arene complexes of transition metals. The synthesis in strong protic acids facilitated obtaining -arene cations of Mn, Re, Ru, Os, Co, Rh and Ir. New nonacidic methods allowed the set of available cationic arene -complexes of Mn, Ru, Rh and Ir to be increased considerably. Based on the developed methods a number of previously unknown binuclear organometallic cations are obtained.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1186–1195, July, 1993.     

Use of γ-γ Coincidence Spectrometry in the Geochemical Study of Diamictites from South Africa

We used - coincidence spectrometry to investigate the possible presence of a meteoritical component in 27 samples of South African diamictites. Recently, several studies have suggested that some tillites/diamictites may represent impact breccias, but a petrographical study by our group found no evidence for the presence of impact-characteristic shocked minerals. The siderophile elements, such as Cr, Co, Ni, and, especially, the platinum group elements, have high abundances in meteorites, but low abundances in terrestrial crustal rocks. The Ir content of the diamictites was measured with the new iridium coincidence spectrometer (ICS) at the University of Vienna, with detection limits of around 0.02 ppb. No enrichments in the contents of Ir and other siderophile elements compared to average crustal concentrations were found; thus, no unequivocal evidence for an impact origin of these diamictites of the South African Dwyka Group can be documented.     

A novel sample decomposition technique at atmospheric pressure for the determination of Os abundances in iron meteorites using isotope dilution inductively coupled plasma-mass spectrometry.

A safe and reliable analytical technique for the determination of Os abundances in ten iron meteorites of various chemical groups was developed using isotope dilution inductively coupled plasma-mass spectrometry coupled with a sample decomposition technique. A major advantage of the sample decomposition technique developed here is that the pressure inside the reaction flask is not increased through the decomposition reaction because the flask is a fully opened system, obviating the risk of explosion of the glass apparatus. Another advantage is that there is no restriction in the sample size being decomposed. In this study, about 2 g of metallic sample were decomposed safely, and this sample size, > 10 times larger than that typically used for the Carius tube technique, allows one to obtain more reliable Os data for heterogeneous samples. The metallic samples were decomposed in a glass flask purged with Ar. Since the O2 was purged from the reaction flask, Os was not oxidised to volatile OsO4, thereby preventing significant evaporation loss of Os. The typical recovery of Os throughout the sample decomposition and separation processes was > 80%, and the total Os blank through the decomposition of a 1 g amount of sample was less than 20 pg. Os abundances were determined by means of stable isotope dilution mass spectrometry using a 190Os-enriched isotopic tracer. Except for Sikhote-Alin, the measured Os abundances in almost all the iron meteorites exhibited a good agreement with the previously published Os abundance data, within the analytical uncertainty achieved in this study (2-5%). For the Sikhote-Alin meteorite, on the basis of a better correlation between Os and Ir abundances, we believe that our Os abundance data should be more reliable. The Os abundance data obtained in this work clearly demonstrated the suitability of the newly developed sample decomposition procedure for low level Os determinations.     

Zur hochspannungselektrophoretischen Trennung anorganischer Ionen unter besonderer Berücksichtigung der Platinmetalle. VI

Zusammenfassung Die hochspannungselektrophoretische Wanderung der Halogenokomplexe der Platinmetalle und verschiedener Metallionen in anorganischen Salzlösungen (NaCl, NaBr, NaJ, NaHSO₄, Na₂SO₄, NaH₂PO₄, NaNO₃, NaBO₂ u. a.) wurde untersucht und im Fall des NaCl die Abhängigkeit der Wanderungsgeschwindigkeitw und der Fleckengröße w von der Elektrolytkonzentration und der Konzentration der Auftragslösung gemessen. U. a. wurde festgestellt, daß die Wanderungsgeschwindigkeiten und Fleckengrößen der Halogenokomplexe und Metallionen von der Art des als Elektrolyt verwendeten Salzes teilweise merklich abhängig sind. So lassen sich in einer 0,1-m NaJ-Lösung die Chlorokomplexe des Os, Ir und Pt gut trennen, wobei für die Wanderungsgeschwindigkeiten die Abstufung gilt: Os > Pt > Ir. Mögliche Ursachen der Abhängigkeiten (Komplexbildungen u. a.) werden diskutiert. Auch wird die Anwendbarkeit verschiedener Salzlösungen für Trennungen an Hand von Beispielen (Pt, Pd, Re, Au; Se, Te, Hg, Os u. a.) gezeigt.

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The high-voltage electrophoretic separation of inorganic ions with special attention to the platinum metals. VI

Summary The high voltage electrophoretic migration of the halogenocomplexes of the platinum metals and various metal ions in inorganic salt solutions (NaCl, NaBr, NaI, NaHSO₄, NaH₂PO₄, NaNO₃, NaBO₂ etc.) was studied and the dependence of the migration velocityw and the spot size w on the electrolyte concentration of the added solution was measured. Among other things it was established that the migration speeds and the spot-sizes of the halogeno complexes and the metal ions are dependent in part and markedly on the kind of salt used as electrolyte. Thus, for instance, the chloro-complexes of Os, Ir and Pt are well separable in a 0.1 molar solution of NaI, whereby the gradation holds Os > Pt > Ir. Possible reasons for the dependencies (complex formations etc.) are discussed. Likewise the applicability of various salt solutions for separations on the basis of examples are shown (Pt, Pd, Re, Au, Te, Hg, Os, and others).

     

Determination of some noble metals in iron meteorites by instrumental neutron activation analysis with a SLOWPOKE reactor

An instrumental neutron activation analysis procedure has been developed which permits the direct determination of Au, Ir, Os and Rh in iron meteorites using a SLOWPOKE reactor. A simple correction method enables the instrumental determination of rhodium using its short-lived nuclide.     

Determination of trace siderophile elements in rock and meteorite samples by radiochemical neutron activation analysis

A simple and effective radiochemical procedure for radiochemical neutron activation analysis (RNAA) of ultra-trace siderophile elements (Ru, Re, Os and Ir) and rare earth elements (REEs) in rock and meteorite samples is presented. To design the procedure, several separation schemes of siderophile elements were examined by using radioactive tracers. By applying the procedure to rock and meteorite samples, we have determined Ru, Re, Os, Ir and REEs, and confirmed that our values were in agreement with the literature values. Our detection limits for Ru, Re, Os, La, Sm and Eu are significantly low compared with those for ICP-MS.     

Neutron activation analysis of rhenium in rocks after preliminary extraction with acetone

A preconcentrating neutron activation method for determination of rhenium in rocks is described. The preconcentration is based on a preliminary extraction separation with acetone. The chemical recovery is determined by an isotope tracer technique using¹⁸⁶Re. The method has been applied to the determination of rhenium in rock samples and extended to more complex systems. Rhenium content is in the range of 110 ppb.     

Bestimmung von Palladium,Iridium und Platin in Silikatgesteinen durch Neutronenaktivierungsanalyse und chemische Abtrennung mit N,N′-Dibenzyl-Dithiooxamid

Palladium, iridium and platinum are determined by neutron activation and chemical separation via¹⁰⁹Pd,¹⁹²Ir and¹⁹⁷Pt. Palladium(II) reacts immediately with N, N-Dibenzyldithiooxamide, Pt(IV) after addition of SnCl₂ and Ir only upon heating in the presence of I. Palladium and platinum are separated together and measured simultaneously on a Ge-X-ray-detector. The chemical yields are determined by spectrophotometry of the extracted complexes. For samples of 0.2g the detection limits amount to 0.02 ppb Pd, 0.5 ppb Pt and 0.002 ppb Ir.     

Spectrophotometric determination of iridium(III) and osmium(VIII) with phenanthrenequinone monoxime after extraction into molten Naphthalene

Summary Conditions have been established for the extraction of iridium (III) and osmium(VIII) as their phenanthrenequinone monoximates into molten naphthalene. The naphthalene is allowed to solidify, separated by filtration, dried with filter paper and dissolved in chloroform. The absorbance is measured at 470 nm for iridium and 475 nm for osmium. Beer's law is obeyed in the concentration ranges 3.2–38.6g of iridium and 1.0–10.9g of osmium in 10 ml of chloroform. The molar absorptivities are 2.3×10⁴ and 8.8×10⁴l. mole^–1.cm^–1 for iridium and osmium respectively. The optimum pH range for the extraction is 4.6–7.4 for iridium and 6.8–10.5 tor osmium. Interferences have been studied in detail and the method successfully applied to various synthetic mixtures. The two metals can be determined sequentially (in the absence of interfering ions), osmium first.

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Spektrophotometrische Bestimmung von Ir(III) und O's(VIII) mit Phenanthrenchinonmonoxim nach Extraktion mit geschmolzenem Naphthalin

Zusammenfassung Die Extraktionsbedingungen für Ir(III) und Os(VIII) als Phenanthrenchinonmonoximate mit geschmolzenem Naphthalin wurden ermittelt. Man läßt das Naphthalin erstarren, filtriert es, trocknet es mit Filterpapier und löst es in Chloroform. Die Absorbanz wird bei 470 nm gemessen für Ir und bei 475 nm für Os. Das Beersche Gesetz gilt für Ir im Konzentrationsbereich 3,2–38,6g und für Os zwischen 1,0 und 10,9g/10 ml Chloroform. Die molare Absorption beträgt 2,3×10⁴ bzw. 8,8×10⁴l·mol^–1·cm^–1 für Ir bzw. Os. Das optimale pH-Gebiet für die Extraktion von Ir liegt bei 4,6–7,4, für Os bei 6,8–10,5. Störungen wurden im Detail untersucht und das Verfahren mit Erfolg für verschiedene Gemische angewendet. In Abwesenheit störender Ionen können Osmium und Iridium hintereinander bestimmt werden.

     

“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.     

The decay of188Re

The -ray spectra of¹⁸⁸Re decay have been studied by using two Ge/Li/ spectrometers and a three parameters /E-E-T/ List coincidence system. The energies and relative intensities of 52 -rays and cascade relations of 14 -rays are determined. Ten new -rays: 155 /633–478/, 984, 1096, 1463, 1332, 1530, 1574, 1810, 1867, and 1937 keV have been identified. The 155 /633–478/ transition is confirmed and its relative intensity is estimated by means of coincidence experiment. 24 levels of¹⁸⁸Re are assigned. Among those, 6 levels are first put into the decay scheme of¹⁸⁸Re. In addition to 1443 keV and 1937 keV levels, 1685, 1729 and 1965 keV levels are also observed in the decay of¹⁸⁸Ir and other reaction studies. The 1948 level is recently suggested in the¹⁹⁰Os/p, t/¹⁸⁸Os reaction. The 486 keV and 811 keV -transitions are also put into the level scheme of¹⁸⁸Re. The ^– decay branching ratio is deduced.     

Synthese,Struktur und Eigenschaften der Komplexe [(Me2PhP)3Cl2Re≡N‐IrCl2(C5Me5)], [(Me2PhP)3Cl2Re≡N‐IrCl(COD)], [PPh4][O3Os≡N‐IrCl2(C5Me5)] und [PPh4][O3Os≡N‐IrCl(COD)] mit Nitridobrücken Re≡N‐Ir und Os≡N‐Ir

Synthesis and Crystal Structures of the Complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)], [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)], [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)], and [PPh₄][O₃Os≡N‐IrCl(COD)] with Nitrido bridges Re≡N‐Ir and Os≡N‐Ir The heteronuclear complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)] ( 1 ), [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)] ( 2 ), [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)] ( 3 ) and [PPh₄][O₃Os≡N‐IrCl(COD)] ( 4 ) were obtained by the reaction of the nitrido complexes [ReNCl₂(PMe₂Ph)₃] and [OsO₃N]^— with the iridium compounds [IrCl₂(C₅Me₅)]₂ and [IrCl(COD)]₂ in benzonitrile. 1 forms red crystals with the composition 1 ·C₆H₅CN in the monoclinic space group P2₁/c and a = 1264.7(2); b = 1945.3(2); c = 1835.4(1) pm, β = 90.35(1)°, Z = 4. The complex fragment [IrCl₂(C₅Me₅)] in the dinuclear complex is connected by an asymmetric nitrido bridge Re≡N‐Ir to the nitrido complex [ReNCl₂(PMe₂Ph)₃]. The nitrido bridge is characterized by a Re‐N‐Ir bond angle of 179.4(2)° and distances Re‐N = 170.9(4) pm and Ir‐N = 203.3(4) pm. 2 forms brownish red, triclinic crystals with the space group P1¯ and a = 1076.6(2), b = 1373.2(2), c = 1452.4(1) pm, α = 107.513(8), β = 101.843(9), γ = 110.04(1)°, Z = 2. The nitrido bridge to the complex fragment [IrCl(COD)] has a Re‐N‐Ir bond angle of 173, 8(4)° and distances Re‐N = 170, 4(8) pm and Ir‐N = 196, 2(8) pm. 3 crystallizes as monoclinic red crystals in the space group P2₁/n and a = 1449.9(2), b = 906.74(4), c = 2628.9(5) pm, β = 103.50(1)°, Z = 4. The nitrido bridge Os≡N‐Ir is slightly bent (Os‐N‐Ir = 165.0(3)°). The distances are Os‐N = 168.3(5) pm and Ir‐N = 201.9(5) pm. 4 forms dark brown, orthorhombic crystals with the space group P2₁2₁2₁ and a = 704.35(2), b = 1228.17(6), c = 3442.0(4) pm, Z = 4. The distances in the slightly bent nitrido bridge (Os‐N‐Ir = 161.8(4)°) are Os‐N = 169.3(7) pm und Ir‐N = 197.8(7) pm.     

Determination of some precious metals by neutron activation analysis

A neutron activation procedure for the determination of Ru, Pd, Os, Ir, Pt and Au in a single irradiation in silicate rocks, meteorites and sulfide ores has been developed. An alkali fusion was used to dissolve and mix 100 to 200 mg powder samples with appropriate carriers. The individual metals were separated and brought to a state of high radiochemical purity by distillation, ion exchange and solvent extraction techniques. Precious metal activities were counted by both γ and β-methods. The procedure was evaluated by replicate analyses of the granite and diabase rock standards, G-1 and W-1 and a Cu−Ni sulfide matte which had previously been analysed by emission spectrographic and spectrophotometric methods. The results were compared with previously published data. A major discrepancy was found only for Ir in W-1.     

Determination of Iridium in Environmental and Geological Samples by NAA with α-Amino Pyridine Resin Preconcentration

The Ir, Au and Pd concentrations in three certified reference materials SARM-7, FC-1 and DZ-1 were determined by neutron activation analysis using -amino pyridine preconcentration. Good agreement between the reference values and our results was obtained, and the reliability of our method was confirmed. This method is suitable for ppb or sub-ppb levels of Ir and Au analyses in environmental and geological samples. The Ir and Au levels in a Chinese coastal sediment GBW07314 were also analyzed.     

Ultra-incompressible Ternary Diborides Re_（0.5）Ir_（0.5）B_2,Re_（0.5）Tc_（0.5）B_2,Os_（0.5）W_（0.5）B_2 and Os_（0.5）Ru_（0.5）B_2：Density Functional Calculation

In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal (P63/mmc) and orthorhombic (Pmmn) structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B (Ru-B) than those of Re-B (Os-B). All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.     

Determination of platinum metals complexes with 2-(6-methyl-2-benzothiazolylazo)-5-diethylaminophenol by reversed-phase high performance liquid chromatography

The use of 2-(6-methyl-2-benzothiazolylazo)-5-diethylaminophenolas a precolumn derivatizing reagent in the reversed-phase high performance liquid Chromatographic separation and determination of Ru(III), Rh(III), Os(IV), Ir(IV), Pt(II), Co(II), Ni(II) and Cu(II) is reported. When the mobile phase consists of methanol-water (76/24% v/v) and 20 mmol/l (pH 5.0) acetate buffer, the eight complexes can be separated within 35 min on a C₈ column. The detection limits are Ru 7.0, Rh 5.1, Os 1.5, Ir 7.6, Pt 3.7, Co 0.62, Ni 0.14 and Cu 1.2 ng/ml, respectively, at a signal-to-noise ratio of 3. RSDs were typically Ca. 1%.