A group separation scheme for radiochemical neutron activation analysis for 24 trace elements in rocks and minerals

A group separation scheme has been developed for radiochemical neutron activation analysis for Ca, Cu, Zn, Ga, Rb, Sr, Zr, Sb, Cs, Ba, La, Nd, Sm, Eu, Gd, Tb, Ho, Tm, Yb, Lu, Hf, Ta, W and Th in a wide variety of silicate rocks and minerals, especially ultrabasic rocks and mafic minerals. The samples are decomposed in a hydrofluoric acid-nitric acid mixture in a PTFE-lined bomb. The soluble fluorides (Cu, Zn, Ga, Rb, Zr, Sb, Cs, Ht, Ta, W and Pa) are separated into three groups of elements by sequential elution from a cationexchange resin. The insoluble fluorides (Ca, Rb, Sr, Cs, Ba and REE) are dissolved and purified from interfering iron and scandium activities by extraction with tri-n-butyl phosphate. If necessary, the four main groups can be purified further from interfering activities such as ⁵⁹Fe, ⁵¹Cr and ⁶⁰Co. The accuracy and reproducibility of the procedure were tested by repeated analysis of U.S. Geological Survey standard granite G-2, andesite AGV-1 and dunite DTS-1.     

Chelatbildende Austauscherharze,VII

Preparation and use of a resin with 1.8-dihydroxynaphthalene-O,O-diacetic acid as chelating group are described. Besides the separation of many of the common interfering ions it also permits the separation of Hf. The following ions could be separated quantitatively: Mg(II), Pb(II), Cu(II), Fe(III), La(III), Ce(IV), Th(IV), Ti(IV), and U(VI). During these and further qualitative and quantitative experiments no interfering ions could be found. A method for the separation of⁹⁵Zr from its daughter nuclide⁹⁵Nb is also described. The main problem proved to be the separation of Zr(IV) and Hf(IV), owing to their close resemblance. To accomplish quantitative determination of Zr and Hf without any separation,⁹⁵Zr and^175+181Hf radioisotopes were used. The chelating resin permits the separation of 95% of Hf(IV) from an equimolar solution. The main part of Hf(IV) is eluated by 2M hydrochloric acid, and subsequently Zr(IV) by 0.75M oxalic acid. The rest of Hf is enriched in the first fractions of the oxalic acid eluate, so that when eliminating these, even after a single step experiment hafnium free from zirconium and a rather pure fraction of zirconium are obtained. Even under extreme conditions of concentration (Zr∶Hf=91∶1) 75% of Hf can be separated free from Zr in a single step experiment.

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Vorgetragen auf der IUPAC-Tagung in Prag, 1967.     

Extraction of U(VI), Zr(IV) and Th(IV) from perchlorate media, by PC-88A

Extraction of U(VI), Zr(IV) and Th(IV) has been investigated from perchlorate media using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC-88A) dissolved in toluene. The extraction of U(VI), Zr(IV) and Th(IV) was found to be quantitative in the pH range 1.6 to 3.2, 2.0 to 4.7 and 2.3 to 3.8, respectively, with 3.0^.10^-3, 5.6^.10^-4 and 1.0^.10^-2M PC-88A dissolved in toluene. U(VI) was stripped with 4.0M HCl, Zr(IV) with 2.5M NaF and Th(IV) with 8.0M HCl from the metal loaded organic phase containing PC-88A dissolved in toluene. The probable extracted species have been ascertained by plotting log D vs. log [HR] as UO₂R₂ ^.2HR, ZrR₄ ^.2HR and ThR₄ ^.4HR, respectively. U(VI) was separated from Zr(IV) and Th(IV) and from other associated metals. This method was proved by the determination of U(VI) in some real samples.     

The quantitative separation of calcium from magnesium,aluminium and other elements by cation-exchange chromatography in ethanol-hydrochloric acid

Magnesium can be separated from calcium by elution with 3.0 M hydrochloric acid containing 60% ethanol from a column of AG₅₀W-X8 cation-exchange resin. Calcium is retained and can be eluted with 3.0 M hydrochloric acid or 2.0 M nitric acid. The separation factor of (α_Mg^ca=5.6 is considerably higher than that in aqueous hydrochloric acid and comparable to those obtained with organic complexing reagents. Separations are sharp and quantitative; up to 10 mmol of magnesium can be separated from 0.01 mmol of calcium and vice versa on a 60-ml column. Al, Fe(III), Mn, Ni(II), Co(II), Zn, Cd, Cu(II), Pb(II), U(VI), Be, Ga, Ti(IV) in the presence of H₂O₂ and many other elements accompany magnesium and can be separated from calcium quantitatively. Sr, Ba, Zr, Hf, Th, Sc, La and the rare earths are retained together with Ca, but can be separated by other methods.     

Precise simultaneous determination of zirconium and hafnium in silicate rocks,meteorites and lunar samples

A precise, sensitive and rapid analytical technique has been developed for the simultaneous determination of Zr and Hf in natural silicate matrices. The technique is based on radiochemical neutron activation analysis and employs a rapid fusion dissolution of the sample and simultaneous precipitation of the Zr−Hf pair with p-hydroxybenzene arsonic acid in an acidic medium. The indicator radionuclides,⁹⁵Zr and¹⁸¹Hf, are counted with a pair of high resolution Ge(Li) detectors and the⁹⁵Zr activity is corrected for the contribution from U fission. The chemical yields of the radiochemical separation are based on Hf carrier, which quantitatively carries both Zr and Hf. The yield is determined by reactivation of the processed samples and standards with a²⁵²Cf isotopic neutron source and by counting the 18.6 sec half-life^179mHf. The sensitivity, precision and accuracy of the procedure are demonstrated by replicate analyses of several standard rocks, meteorites and lunar samples which exhibit a wide range of Zr and Hf abundances.     

Vibrational spectra and structure of zirconium and hafnium cyclopentadienyl hydrides

Raman and IR spectra (4000-50 cm^–1) of solid cyclopentadienyl zirconium and hafnium hydrides Cp₂MH₂, Cp₂MD₂, Cp₂Zr(H)X, and Cp₂Zr(D)X (Cp = ⁵-C₅H₅; M = Zr, Hf; X = Cl, Br) have been studied. The vibrational modes of MH groups, Cp-rings, and metal-ligand bonds are discussed and the band assignments are proposed. In the solid state, these complexes form polymers with linear hydride bridges of the M-H-M type. The force constants of the M-H and M-Cp bonds increase on going from Zr to Hf.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1604–1609, September, 1994.     

INAA of IAEA-331 (spinach), SRM,for 40 elements

Forty elements in IAEA-331 (Spinach), an intercomparison material, have been determined using NAA. Among them, 30 elements, Ag, Al, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Eu, Fe, Hf, K, La, Mg, Mn, Na, Ni, Rb, Re, Sc, Se, Sr, Ta, Tb, Th, V, Zn and Zr were determined by INAA. A series of simple and quantitative radiochemical separation procedures were established for the determination of ten additional elements. Cd, Lu, Mo, Sb, Sm, Yb, U were determined by removing the major interfering nuclide⁸²Br. Cu was determined by 0.048M NaDDTC/CHCl₃ extraction from 1M HCl medium. As and P were determined using an inorganic exchange column of acid aluminium oxide (AAO). Integral counts from 80 keV to 130 keV contributed by Bremsstrahlung from³²P -were used to evaluate the content of phosphorus.     

High performance liquid chromatographic separation of <Superscript>228,229</Superscript>Th and <Superscript>232,233</Superscript>U and their estimation by α- and γ-ray spectrometry

The activities of ^228,229Th and ^232,233U from an irradiated ThO₂ sample were radiochemicaly separated by using high performance liquid chromatography. Plancheted sources of the separated samples were made and the amount of ^232,233U and ^228,229Th were estimated by using alpha and gamma-ray spectrometric techniques. These estimations are important for the Th–U fuel reprocessing cycle of advanced heavy water reactor and accelerator driven sub-critical system.     

Rapid sample digestion by fusion and chemical separation of Hf for isotopic analysis by MC-ICPMS

A new method for rapid sample digestion and efficient chemical separation of Hf and REE from rock samples for precise isotopic analysis is presented. Samples are digested by fusion in the presence of a lithium borate flux at 1100 °C and dissolved whilst molten in dilute nitric or hydrochloric acid. Prior to chemical separation using ion exchange techniques, Li and B from the flux material and Si from the sample are separated from the remaining major elements, REE and high field strength elements (HFSE) in the sample by Fe-hydroxide co-precipitation. The chemical separation of Hf is a two-stage procedure designed to first remove the remaining matrix elements (e.g. Fe, Ba) in the sample using standard cation exchange techniques, followed by separation of Hf from the REE and HFSE on TEVA extraction chromatographic resin. Hf yields are >90% and total procedural blanks are ca. 50 pg. Hf isotope ratios of a synthetic standard solution and replicate digestions of international rock standards BHVO-1 and BCR-1 measured on multi-collector inductively coupled plasma mass spectrometer (MC-ICPMS) reproduce similarly to ≤50 ppm (2 S.D.). The following elemental ratios are routinely obtained for elements, which interfere isobarically or may affect the ionisation and/or fractionation behaviour of Hf during analysis: ¹⁷⁶Yb/¹⁷⁶Hf<0.0001; ¹⁷⁶Lu/¹⁷⁶Hf<0.00001; Ti/Hf<0.05. This technique also provides a means of separating Nd from the REE fraction for isotopic analysis and, potentially, may be adapted for measurement of Lu/Hf ratios by isotope dilution techniques.     

A chelating resin containing 1-(2-thiazolylazo)-2-naphthol as the functional group; synthesis and sorption behavior for trace metal ions

A new polystyrene-divinylbenzene resin containing 1-(2-thiazolylazo)-2-naphthol (TAN) functional group was synthesized and its sorption behavior for 19 metal ions including Zr(IV), Hf(IV) and U(VI) was investigated by batch and column experiments. The chelating resin showed a high sorption affinity for Zr(IV) and Hf(IV) at pH 2. Some parameters affecting the sorption of the metal ions are detailed. The breakthrough and overall capacities were measured under optimized conditions. The overall capacities of Zr(IV) and Hf(IV) that were higher than those of the other metal ions were 0.92 and 0.87 mmol/g, respectively. The elution order of metal ions at pH 4 was evaluated as: Zr(IV)>Hf(IV)>Th(IV)>V(V)>Nb(V)>Cu(II)>U(VI)>Ta(V)>Mo(VI)>Cr(III)>Sn(IV)>W(VI). Quantitative recovery of most metal ions except Zr(IV) was achieved using 2 M HNO₃. Desorption and recovery of Zr(IV) was successfully performed with 2 M HClO₄ and 2 M HCl.     

Adsorption of several tracer cations and separation of234Th from238U and113mIn from113Sn on tin dioxide

The uptake of 22 cations at tracer concentrations has been studied over hydrous tin dioxide exchanger material. A granular variety of tin dioxide was prepared from the reaction of tin(IV) chloride with NaOH solution, and the formula of the material was ascertained to be SnO₂·1.7 H₂O. Radiochemical separation of carrier-free²³⁴Th from²³⁸U and^113mIn from¹¹³Sn was achieved over a tin dioxide column. The separated products were of high radionuclidic purity. The overall separation procedures are very simple and quick with quantitative yield.     

Separation of metallic impurities from uranium by anion exchange on Dowex 1×8 resin

The separation of metallic impurities from uranium by anion exchange with a Dowex 1×8 resin has been investigated. The following elements can be quantitatively separated from 400 mg uranium using a 1 cm diameter 15 or 30 cm long column. The elements Ag, Al, Ba, Ca, Cr, Cs, K, Mg, Mn, Na, Ni, Rb, REE, Sc, Th, Ti and Y can be separated by eluting the elements with conc. HCl. Uranium is retained by the resin. Al, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Na, REE and V can be separated by eluting with 0.01 N H₂SO₄. Uranium is retained by the resin. Cd and Zn can be separated by first eluting uranium with 0.5 N HCl and then eluting Cd and Zn with 1 N NH₃. Hf, Zr and V can be separated by eluting with 5 N HCl but some uranium contamination is unavoidable.     

Separation of trivalent rare earths plus sc(iii) from al,ga,in,tl, fe,ti, u and other elements by cation-exchange chromatography

A method is presented for the quantitative separation of the trivalent rare earths plus Sc(III) as a group from Al(III), Ga(III), In(III), Tl(III), Fc(III). Ti(IV), U(VI), Be(II). Mn(II), Co(II), Cu(II), Ni(II). Zn(II). and Cd(II). These elements can be eluted from a cation-exchange column with 1.75 N HCl, while the rare earth group elements are retained. Numerous other elements not investigated have low distribution coefficients in 1.75 N HCl and therefore should be separated by the same procedure; Th(IV) is retained by the column when the rare earths are elutcd with 3.0 N HCl. The only elements which partially accompany the rare earths plus Sc(III) are Zr(IV), Hf(IV), Sr(II), and Ba(II) ; these have to be separated by special procedures. The method is suitable for accurate reference analysis over a wide range of concentrations.     

Towards the development of a fossil bone geochemical standard: an inter-laboratory study

Ten international laboratories participated in an inter-laboratory comparison of a fossil bone composite with the objective of producing a matrix and structure-matched reference material for studies of the bio-mineralization of ancient fossil bone. We report the major and trace element compositions of the fossil bone composite, using in-situ method as well as various wet chemical digestion techniques.For major element concentrations, the intra-laboratory analytical precision (%RSD_r) ranges from 7 to 18%, with higher percentages for Ti and K. The %RSD_r are smaller than the inter-laboratory analytical precision (%RSD_R; <15-30%). Trace element concentrations vary by ∼5 orders of magnitude (0.1 mg kg⁻¹ for Th to 10,000 mg kg⁻¹ for Ba). The intra-laboratory analytical precision %RSD_r varies between 8 and 45%. The reproducibility values (%RSD_R) range from 13 to <50%, although extreme value >100% was found for the high field strength elements (Hf, Th, Zr, Nb). The rare earth element (REE) concentrations, which vary over 3 orders of magnitude, have %RSD_r and %RSD_R values at 8-15% and 20-32%, respectively. However, the REE patterns (which are very important for paleo-environmental, taphonomic and paleo-oceanographic analyses) are much more consistent.These data suggest that the complex and unpredictable nature of the mineralogical and chemical composition of fossil bone makes it difficult to set-up and calibrate analytical instruments using conventional standards, and may result in non-spectral matrix effects. We propose an analytical protocol that can be employed in future inter-laboratory studies to produce a certified fossil bone geochemical standard.     

Laser-ablation ICP-MS analysis of siliceous rock glasses fused on an iridium strip heater using MgO dilution

Trace element determination in rocks by fusion on an iridium strip heater followed by LA-ICP-MS analysis of the glass beads is extended here to SiO₂-rich rocks; rapid fusion of samples with >55 wt% SiO₂ is facilitated by dilution by high purity MgO. The method developed here can rapidly and accurately determine numerous trace elements in a large range of rock compositions in a short time (about 50 samples/day). Systematic evaluation for a large range of rock compositions (natural rocks and reference materials AGV-2, GSP-2, JG-1a) with SiO₂ contents between 45 and 80 wt% shows that reproducibility and accuracy within 10% can be routinely achieved for most of the 28 trace elements investigated (Rb, Sr, Cs, Ba, Ti, Zr, Hf, Nb, Ta, Sc, V, Cr, Ni, Pb, Th, U, REE). The 40 mg sample size is smaller than for XRF, INAA or solution-ICP-MS, detection limits are lower, and trace element palettes more complete than XRF and INAA. This microchemical method is thus attractive for the analysis of all natural geological materials as well as for experimental applications with small samples. Samples with SiO₂-contents >55 wt% require hot and long melting to achieve homogeneous glasses and eliminate all residual minerals, particularly refractory accessory phases. Melting conditions of 1600 °C and 20 s for samples are recommended for SiO₂ contents between 55 and 70 wt%, whereas 1800 °C and 20–30 s are often required for samples with >70 wt% SiO₂. Problems are encountered for Pb and Cs due to volatilization on the Ir strip, for Sc due to interferences, and Zr and Hf due to their sequestration in refractory accessory minerals. Correspondence: Franziska Nehring, Department of Geosciences, University of Mainz, Becherweg 21, 55099 Mainz, Germany     

Determination of rare earths and other trace elements in samples of Antarctica by neutron activation analysis

The concentrations of REE and other trace elements have been determined in samples of Antarctica by Instrumental Neutron Activation Analysis (INAA). The samples were collected from the West Lake area near Great Wall Station. The samples include sediment, residual plants, rock and soil taken from the bottom of the lake to 3.4 m deep. The amounts of samples were very rare. In order to get more information, reactor NAA using both short and long irradiations with K₀ standardization has been adopted. Nine rare-earth elements (REE) namely La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, and Lu as well as other trace elements (As, Au, Ba, Br, Co, Cr, Hf, Sc, Se, Th, V, Zn) have been determined. The concentrations and distribution patterns of REE in the samples have been given.     

Separation of Zr in the rubble waste generated at the Fukushima Daiichi Nuclear Power Station

Separation method of Zr using trans uranium resin (TRU resin) and tetra valent actinide resin (TEVA resin) was developed for the analysis of ⁹³Zr contained in the rubble waste. Zr, Nb, and U were quantitatively extracted on the TRU resin from 3 M HNO₃ and striped with 0.01 M HF, in addition, some part of Mo, Hg, Bi, and Th were also included in the stripping solution. The stripping solution was evaporated to eliminate HNO₃ and the residue was dissolved in 0.1 M HF. Finally, Zr was separated from Nb and Mo with the TEVA resin.     

Synergism in the Solvent Extraction of Tetravalent Metal Ions. A Study of the Formation of the Synergistic Adducts

β-diketone complexes of the type M(LL)₄, where M = Zr(IV), Hf(IV), Th(IV) and U(IV), and LL = β-diketone with different acid strengths, viz. acetylacetone, dibenzoylmethane, thenoyltrifluoroacetone, trifluoroacetylacetone and hexafluoroacetylacetone were used to prepare adducts of the type M(LL)₄ · S, where represents the neutral phosphorus esters with various basicities, viz. tributylphosphate, trioctylphosphine oxide, triphenylphosphine oxide and triphenylphosphate. It was found that no adducts of the Zr(IV), Hf(IV) and U(IV) complexes were formed Adducts of the Th(IV) complexes were formed only if the β-diketones were relatively strong acids, e. g. thenoyltrifluoroacetone, trifluoroacetylacetone and hexafluoroacetylacetone. Results of the attempted preparations showed that the possibility of adduct formation between β-diketone complexes and phosphorus esters in influenced by the acid strength od the β-diketone, the basicity of the phosphorus ester, the ionic radii, and the electron configuration of the metal.     

Cation-exchange studies of yttrium(III) and its separation from various other elements

Summary Systematic studies are presented on the cation-exchange behaviour of yttrium on Dowex 50W-X8. HCl, HNO₃, H₂SO₄, NH₄Cl, NH₄NO₃, (NH₄)₂SO₄, CH₃COONH₄, NaCl, NaNO₃, malonic acid, tartaric acid and EDTA were used as eluting agents. Y was separated from a large variety of elements by selective elution or selective adsorption. Thus it was possible to separate it from many common ions such as alkalis, alkaline earths, Bi, Hg, V, Cd, U, In, Co, Ga, Zn, Sc, Fe, Al, Ni, and Ce by selective elution. It was separated from Ti, Zr, Hf, and Sb by selective sorption in citrate media and from Cr, Tl, Pb, and Th by gradient elution.     

Multi-element determination in sandstone rock by instrumental neutron activation analysis

Summary Instrumental neutron activation analysis (INAA) was used for the qualitative and quantitative analysis of sandstone samples of Aswan area, in South Egypt. The samples were properly prepared together with standards and simultaneously irradiated by a neutron flux of 7 ^. 10¹¹ n ^. cm^-2.s^-1. in the TRIGA research reactor facilities in Mainz. The gamma-spectra from a hyperpure germanium HPGe detector were analyzed. The present study provides the basic data of elemental concentrations of a sandstone rock. The following elements have been determined: Na, K, Fe, Sc, Cr, Co, Zr, Ce, La, Nd, Sm, Eu, Yb, Lu, Hf, Ta, Th and U. Energy dispersive X-ray fluorescence (EDXRF) was used for comparison and to detect elements which can be detected only by this method.