Determination of gold, platinum and palladium in geological samples by inductively coupled plasma-mass spectrometry after separation and preconcentration with C-410 anion exchange resin

A method for the determination of Au, Pt and Pd in geological samples is described. Au, Pt and Pd can be separated and concentrated quantitatively by C-410 anion-exchange resin in the condition of 1.5 mol/L HCl with the adsorption rates of 91.2%, 100.0% and 95.7% respectively. No interference exists from coexisting elements except for Ge(IV), Cr(VI),Ti(IV) in inductively coupled plasma-mass spectrometry. The detection limits are 0.27 mug/L, 0.40 mug/L and 0.19 mug/L for Au, Pt and Pd respectively. The results of these elements in standard geological materials are in agreement with certified values with precision of 19.2% RSD for Au (n = 8), 28.1% RSD for Pt (n=8), and 15.6% RSD for Pd (n=8).

New technique for capillary electrophoresis directly coupled with end-column electrochemiluminescence detection

capillary electrophoresis (CE) is characterized. A 300 mum diameter Pt working electrode was used to directly couple with a 75 mum inner diameter separation capillary without an electric field decoupler. The hydrodynamic cyclic voltammogram (CV) of Ru(bpy)(3)(2+) showed that electrophoretic current did not affect the ECL reaction. The presence of high-voltage (HV) field only resulted in the shift of the ECL detection potential. The distance of capillary to electrode was an important parameter for optimizing detection performance as it determined the characteristics of mass transport toward the electrode and the actual concentration of Ru(bpy)(3)(2+) in the detection region. The optimum distance of capillary to electrode was decided by the inner diameter of the capillary, too. For a 75 mum capillary, the working electrode should be placed away from the capillary outlet at a distance within the range of 20-260 mum. The effects of pH value of ECL solution and molecular structure of analytes on peak height and theoretical plate numbers were discussed. Using the 75 mum capillary, under the optimum conditions, the method provided a linear range for tripropylamine (TPA) between 1 x 10(-10) and 1 X 10(-5) mol/L with correlation coefficient of 0.998. The detection limit (signal-to-noise ratio S/N = 3) was 5.0 x 10(-11) mol/L. The relative standard deviation in peak height for eight consecutive injections was 5.6%. By this new technique lidocaine spiked in a urine sample was determined. The method exhibited the linear range for lidocaine from 5.0 x 10(-8) to 1.0 X 10(-5) mol/L with correlation efficient of 0.998. The limit of detection (S/N = 3) was 2.0 x 10(-1) mol/L.

Hydrothermal synthesis and characterization of bimetallic cluster complex [{Mn(phen)(2)}(2)V4O12]center dot 1/2 H2O

A new bimetallic cluster complex with the formula [(Mn(phen)(2))(2)V4O12].1/2 H2O has been synthesized through hydrothermal reaction of vanadate staring material with manganese cation in the presence of nitrogen donor chelating ligand and characterized by single-crystal X-ray diffraction, elemental analysis, IR UV-vis, ESR spectrum and thermal analysis. The compound crystallize in the monoclinic space group P2(1)/c with a = 18.475(4) Angstrom, b = 11.473(2) Angstrom, c = 23.667(5) Angstrom, beta = 97.76(3)degrees, V = 4971(2) Angstrom(3) and Z = 4. The structure of [{Mn(phen)(2)}(2)V4O12].1/2 H2O is composed of a discrete V4O124- cluster covalently attached to two [Mn(phen)(2)](2+) fragments.

Hydrothermal synthesis and X-ray single crystal structure of bimetallic cluster complex [{Co(phen)(2)}(2)V4O12]center dot H2O

A new bimetallic cluster complex with the formula [{Co(phen)(2)}(2)V4O12](H2O)-H-. was synthesized from the hydrothermal reaction of V2O5, H2C2O4, Co(NO3)(2), 1,10-phenanthroline (phen), (C4H9)(4)NOH and water. The compound crystallizes in an orthorhombic system with space group Pbcn and unit cell parameters a = 19.106(3) Angstrom, b = 15.250(3) Angstrom, c = 16.321(2) Angstrom, V = 4755.4(13) Angstrom(3), Z = 4 and R = 0.0318. The bimetallic cluster complex [{Co(phen)(2)}(2)V4O12](H2O)-H-. is composed of a discrete V4O124- cluster eovalently attached to two [Co(phen)(2)](2+) fragments and the discrete hexanuclear bimetallic clusters of [{Co(phen)(2)}(V4O12)-V-2](H2O)-H-. are further extended into interesting three-dimensional supermolecular arrays via pi-pi stacking interactions of phen groups. Other characterizations by elemental analysis, IR, and thermal analysis are also described.

Matrix effects in flow injection-inductively coupled plasma mass spectrometry

Matrix effects in now injection (FI) inductively coupled plasma mass spectrometry has been studied,and the results have been compared with those of continuous nebulization. The matrix element As and nu with higher ionization potential ( > 9eV) have enhancement effect on the analyte signal,and the heavier the analyte mass, the smaller the enhancement effects by Fl. The matrix elements Cu, In, Li, Na and Pb with lower ionization potential have suppression effect on the analyte signal. The heavier the matrix element mass, the more severe the suppression effects. The heavier the analyte mass, the smaller the suppression effects. The higher ionization potential of analyte, the more severe the suppression effects. Compared with continuous nebulization, the degree of suppression effect is smaller and the degree of the enhancement effect is larger by Fl.

Synthesis and structure of molybdenum-citrato cluster mu(2)-S bridge

A new molybdenum-citrato cluster containing [Mo2O2(mu-S)(2)(C6H5O7)(C6H4O7)](5-) anion was synthesized and characterized by elemental analysis, IR, UV-Vis spectra, XPS and X-ray diffraction. The parameters of the crystal structure of the compound are monoclinic, space group P2(1)/c, a = 2. 376 6(5) nm, b = 1. 327 4(3) nm, c = 2. 247 1(5) nm, beta = 118. 21 degrees, V = 6. 247(2) nm(3), Z = 8, D-c = 2. 128 g/cm(3), F(000) = 3 984, mu = 1 694 cm(-1), R = 0. 083 1 and R-2,R-w = 0. 154 9. The anion is binuclear molybdenum-citrato complex with mu(2)-S bridge. Each molybdenum atom pocesesses a distorted octahedral struture, which is coordinated with a terminal oxygen, two sulfur atoms, three oxygen atoms of hydroxyl, alpha-carboxylate, beta-carboxylate from citrate.

Matrix effects in inductively coupled plasma mass spectrometry by use of organic solvents

Matrix effects arising from ethanol, propanol, glycerol, acetic acid, ethylenediamine and triethanolamine in inductively coupled plasma mass spectrometry have been studied. Addition of ethanol, propanol, glycerol, acetic acid, ethylenediamine and triethanolamine into solution has an enhancement effect on the signal intensity of analyte with ionization potential between 9 and 11 eV. The ethylenediamine and triethanolamine have higher enhancement effect on the signal intensity of Hg than that of ethanol, propanol, glycerol and acetic acid. Addition of ethylenediamine and triethanolamine into solution has a suppression effect on the signal intensity of Ph and Sr. The mechanism of the enhancement or suppression was investigated. The signal enhancement of Hg in the presence of ethylenediamine and triethanolamine is not caused by improved degree of ionization of Hg and nebulization efficiency. The suppression effects of Ph and Sr in the presence of ethylenediamine and triethanolamine are due to decrease of atomization efficiency of these elements. A method for the determination of Hg in the biological standard samples Ly ICP-MS was developed.

Determination of ultra-trace rare-earth elements in human plasma by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS),a highly sensitive inorgnic analytic technique,fits to determine ultra-nace rare-earth elements in human plasma. Under the optimized conditions detection limits for 15 rare-earth elements are in the range of 0.7 (for Eu)-5.4 (for Gd) ng.L-1. Indium as an internal standard element is used to compensate for matrix suppression effect and sensitivity drift. Three kinds of preparation methods, diluted with 1% HNO3, digested with HNO3-H2O2 and with HNO3-HClO4, are checked and compared,and the former is the simplest way to be measured. The samples diluted with 1% HNO3, stored in 4 degrees C, are very steady for 16 days. With the method, 11 healthy plasma samples in Changchun area of China are analysed.

Hydrothermal synthesis and crystal structure of [{Cu(2,2 '-bpy)(2)}(2)Mo8O26]: a beta-octamolybdate cluster covalently bonded to two {Cu(2,2 '-bpy)(2)}(2+) coordination complexes via bridging oxo groups

An organic-inorganic hybrid solid, (Cu(2,2'-bpy)(2))(2)Mo8O26, has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Dark green crystals crystallize in the orthorhombic system, space group Pna21, a = 24.164(5), b = 18.281(4), c = 11.877(2) Angstrom, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, V= 5247(2) Angstrom (3), Z = 4, lambda (MoK alpha) = 0.71073 Angstrom (R(F) = 0.0331 for 5353 reflections). Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.69 degrees < theta < 25.04 degrees using the omega -scan technique. The structure was solved by the direct method and refined by full-matrix least squares on F-2 using SHELXL-93. The structure of this compound consists of discrete (Cu(2,2'-bpy)(2))(2)Mo8O26 clusters, constructed from beta -octamolybdate subunits ((Mo8O26)(4-)) covalently bonded to two (Cu(2,2'-bpy)(2))(2+) coordination complexes via bridging oxo groups that connect two adjacent molybdenum sites. (C) 2001 Academic Press.

New typical ionic cluster K+(KNO3)(n) and NO3-(KNO3)(m)

New typical ionic clusters with complex anions could be formed directly from the KNO3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO3 being 101 in the full mass spectrometry of the positive-ion and the negative-ion. The general formula of the ionic clusters belonged to K+(KNO3)(n) and NO3- (KNO3)(m).

Application of inductively coupled plasma mass spectrometry in biological samples analysis

Recent important applications of inductively coupled plasma mass spectrometry in biological samples analysis are reviewed. The sample preparation, sample introduction techniques, interference correction and typical applications are introduced in detail with 154 references.

Characteristics in frequency domain by inductively coupled plasma atomic emission spectrometry with charge injection detection

The charactesistics of two-dimension spectra obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES) with charge injection detection (CID) in frequency domain were studied in the present paper. The measurement spectra were Fourier transformed and the frequency distribution of the spectra was obtained. Results showed that the spectra in frequency domain could he divided into two parts:high frequency and low frequency signals. The later stood for measurement spectra and the former for background and noises. However, the high frequecny signals could not be smoothed simply to reduce noises because the background was deteriorated even though the spectral signal did not change significantly.

Determination of the impurities elements in high-purity cadmium by inductively coupled plasma mass spectrometry

A method for the determination of impurity elements in high purity cadmium by inductively coupled plasma mass spectrometry was developed. The spectral interference arising from Cd was discussed and the magnitude of interference by the polyatomic ion of Cd was compared. The effect of the high concentration Cd on the analyte signal was studied. The results showed that Cd possessed both significant suppression effects on the light mass elements signal and enhancement effects on the heavy mass elements signal,and the effects can be corrected by the use of internal standard elements. In this paper, Y and Bi was employed for the light mass elements and the heavy mass elements,respectively. As, Be, Co, Cu, Ga, Ge, Mn, Mo, Pb, Ni, Sr, Au, Tl, Th, V and U in high purity cadmium were determined. Detection limits are 0.005-0.052 mu g L-1,and the recoveries of standard addition are 82%-108%.

Determination of mercury in biological samples using organic compounds as matrix modifiers by inductively coupled plasma mass spectrometry

A method was developed for the determination of total mercury in biological samples. The effects of aqueous ammonia, ethylenediamine and triethanolamine on Hg signal intensity by inductively coupled plasma mass spectrometry has been evaluated and the possible mechanisms discussed. It has been proved that the signal intensity of Hg significantly increases with adding, in the presence of small amounts of aqueous ammonia, ethylenediamine or triethanolamine. The normalized intensity (the signal intensity ratio with amine and without amine) of Hg increases as the concentration of aqueous ammonia, ethylenediamine or triethanolamine increases, but the degree of enhancement of aqueous ammonia was smaller than that of ethylenediamine and triethanolamine. The normalized intensity of Hg with aqueous ammonia, ethylenediamine and triethanolamine decreases as the nebulizer flow rate increases, but decreasing degree of aqueous ammonia was smaller than that of ethylenediamine and triethanolamine. The higher the RF powers the higher the normalized intensity of Hg at the same nebulizer flow rate. The addition of aqueous ammonia, ethylenediamine and triethanolamine into analytical solutions significantly improved the transport efficiency of Hg. The detection limit of Hg is improved about ten times by the addition of ethylenediamine or triethanolamine under the optimum experimental parameters. The method has been used to determine mercury in biological standard reference materials (SRM). The analytical results are very close to the certified values and the determined values for similar samples.

Factor analysis used to peak position optimization and spectral interference correction in inductively coupled plasma atomic emission spectrometry

Target transformation factor analysis was used to correct spectral interference in inductively coupled plasma atomic emission spectrometry (ICP-BES) for the determination of rare earth impurities in high purity thulium oxide. Data matrix was constructed with pure and mixture vectors and background vector. A method based on an error evaluation function was proposed to optimize the peak position, so the influence of the peak position shift in spectral scans on the determination was eliminated or reduced. Satisfactory results were obtained using factor analysis and the proposed peak position optimization method.