Infrared laser ablation study of pressed soil pellets with inductively coupled plasma atomic emission spectrometry.

Potential of infrared laser ablation (LA) coupled with ICP-AES as a technique suitable for the determination of trace elements (Zn, Cu, Ni, Cr, and V) in agricultural soils was studied. Operating parameters such as laser beam energy, laser beam focusing with respect to the sample surface, and velocity of the sample translation in the plane perpendicular to the laser beam were optimized. Soil samples were mixed with powdered Ag as a binder, and an internal standard (GeO(2)), and pressed into pellets. Calibration samples were prepared by adding known amounts of oxides of elements of interest into soils of known elemental composition and then processed in the same way as the analyzed samples. Calibration curves were found to be linear at least up to several hundreds of mg kg(-1) for the elements of interest. The elemental contents obtained by using LA-ICP-AES were compared with those obtained by analysis using wet chemistry followed by ICP-AES with pneumatic nebulization (PN). The results were in good agreement. Accuracy was also tested using certified reference soils with a bias not exceeding 10% relative.

Calibration graphs for steels by IR laser ablation inductively coupled plasma atomic emission spectrometry.

Infrared laser ablation (IRLA) was studied as a sample-introduction technique for the analysis of steels by inductively coupled plasma atomic emission spectrometry (ICP-AES). A comparison of two IRLA-ICP-AES systems based on Q-switched nanosecond Nd: YAG lasers was performed. The beam of the LINA-Spark atomizer (LSA Sarl, Cully, Switzerland) based on the Surelite 1-20 laser (Continuum, USA) was moved along a circle. A Perkin-Elmer Optima 3000 DV ICP system was used both with lateral and axial viewing modes. A laboratory-made ablation system based on the Brilliant laser (Quantel) was coupled to a Jobin-Yvon 170 Ultrace ICP (lateral viewing, polychromator part employed). A sample was rotated along a circle during ablation. Linearity of calibration plots was verified at least up to 19% Cr and 12% Ni without internal standardization for both LA-ICP-AES systems. Other elements examined were Mo up to 3%, Mn up 1.5%, Si up to 1.7%, and Cu up to 0.15%. The reproducibility was in the range 5-1 %RSD for a mass percentage 0.5-20% of steel constituents. The relative uncertainty of the centroids of the calibration lines was in the range from +/- 4% to +/- 12% for Cr, Ni, Mn, Mo, and Si, and from +/- 8% to +/- 19% for Cu. The lowest determinable quantities were calculated for calibration dependencies. Performances of both the IR-LA-ICP-AES were comparable.

Calibration graphs for Ti, Ta and Nb in sintered tungsten carbide by infrared laser ablation inductively coupled plasma atomic emission spectrometry.

Infrared laser ablation (IR-LA) has been studied as a sample introduction technique for the analysis of sintered cobalt-cemented tungsten carbide materials by inductively coupled plasma atomic emission spectrometry (ICP-AES). Fractionation of cobalt was observed. Linearity of calibration plots was verified at least up to 15% Ti, 8% Ta, and 3% Nb. Above 1% (m/m) Ti, Ta, and Nb, the repeatability of results was better than 3% R.S.D. The relative uncertainty at the centroid of the calibration line was in the range from +/- 3% to +/- 4% for Ti, Ta, and Nb with internal standardization by tungsten and up to +/- 5% without internal standardization. The limits of detection were 0.004% Ti, 0.001% Ta, and 0.004% Nb. Elimination of the cemented hardmetal dissolution procedure is the main advantage of this method.

Depth profiling of tin-coated glass by laser ablation inductively coupled plasma emission spectrometry with acoustic signal measurement.

A pulsed, frequency-quadrupled Nd:YAG laser (266 nm, 10 Hz) coupled to an inductively coupled plasma atomic emission spectrometer (ICP-AES) was employed for depth profiling by ablation of a pyrolytically deposited Sn layer (300 nm) on float glass. The procedure consisted of performing individual ablation cycles (layer-by-layer). A raster with stroke distance of either 50 microm or 200 microm (the raster density) was used as an ablation pattern. The ablation was stopped after each cycle and the peak area of the resulting transient optical signal of the ICP discharge was plotted against the cycle number. The ablation rate of 90 to 20 nm per cycle at a low-energy pulse (6 mJ to 1 mJ) was determined by profilometry. A beam masking was employed to attenuate the laser shot energy and to eliminate the peripheral irregularity of the beam profile. Almost uniform removal of the square area (1 mm x 1 mm) of the coating by ablation was achieved by combining the fitted raster density, beam masking, focusing and beam energy. Different ablation processes were distinguished in cases of the tin coating and the uncoated glass surface. While the coating was mainly evaporated, the uncoated glass surface exhibited a crumbling associated with production of glass powder. This was confirmed by electron microscopy observations. The measured acoustic signal followed the behavior of the emission intensity of the Sn line and was supposed to be proportional to the amount of Sn vapors. The emission intensity depth profile of the Sn coating with graded structure was obtained, which qualitatively corresponded with the depth profile measured by secondary ion mass spectrometry.

Preconcentration of platinum group metals on modified silicagel and their determination by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry in airborne particulates.

Modified silicagel (C18) was studied for separation and preconcentration of platinum group metals (Ru, Rh, Pd, Os, Ir and Pt) as ion associates of their chlorocomplexes with cation of onium salt N(1-carbaethoxypentadecyl)-trimethyl ammonium bromide. Sample containing HCl and the onium salt was pumped through the column. After elution with ethanol the eluate was evaporated in the presence of HCl. Resulting aqueous solutions were analysed with inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Recovery values of 1-20 mug Pt and Pd from 50 ml of synthetic pure solution were 100+/-3 and 100+/-1%, respectively, however, they diminished with increasing sample volume and in the presence of the real sample matrix or nitrate ions. Samples of engine soot (NIES No. 8), decomposed by low pressure oxygen high-frequency plasma, and airborne particulates from dust filters of meteorological stations, leached with HNO(3) and H(2)O(2), were analysed. A reasonable agreement was found between ICP-MS and ICP-AES results for airborne dust samples and the values comparable with those in literature were determined in NIES No. 8.

Comparison of some analytical performance characteristics in inductively coupled plasma spectrometry of platinum group metals and gold.

The limits of detection, precision and matrix effects in the inductively coupled plasma spectrometry of platinum group metals (PGMs) and gold were measured and evaluated for four ICP-AES and one ICP-MS instrument. The sample matrix was a cationic surfactant used for the PGMs and gold preconcentration on a modified silica gel (C18). A sorption of ion associates of PGMs and gold chlorocomplexes with the cation of onium salt N(1-carbaethoxypentadecyl)-trimethyl ammonium bromide was considered. The calibration curves, limits of detection and matrix effects were evaluated in the presence of 0.003 mol dm(-3) of onium salt (1.3 mg cm(-3)) and 0.1 mol dm(-3) HCl. The values of limits of detection (3 sigma(bl)) of PGMs for all axial ICP instruments were mostly below 10 ng cm(-3). Lateral observation on dual view ICP instrument yielded only 3 times higher detection limits in comparison to the axial mode of the same spectrometer and the detection limits for ICP-MS instrument were on the levels of units or tens of pg cm(-3). These limits of detection did not significantly differ from values obtained with pure solutions. Matrix effects in the presence of onium salt did not exceed 12% depression in the analytical signals. Besides the coefficients of correlation, the uncertainties on centroids of concentrations were calculated for calibration graphs obtained by linear regression.

Selective preconcentration of thallium on modified silica gel for its determination by flame emission and absorption spectrometry.

Thallium (0.02-20 mug) was successfully preconcentrated on silica gel C18 from 0.1M hydrochloric acid in the presence of various cationic surfactants as ion pairs with tetrachlorothallate(III), and subsequently eluted with 96% ethanol. Of various atomic spectrometric procedures considered, emission spectrometry in a nitrous oxide-acetylene flame is suitable for the final determination of thallium in plants, this is more sensitive for thallium than flame atomic absorption spectrometry.

Determination of platinum in plants by emission spectrometry after preconcentration on modified silicagel.

Silicagel Separon SGX C18 (particle size 7 microm) was suitable for the preconcentration of 2-20 microg of Pt from 0.1M hydrochloric acid in the presence of cationic surfactants especially dimethyllaurylbenzylammonium bromide, with subsequent elution with 96% ethanol. The recovery was 86-110% for 2 microg of Pt. The sample matrix corresponding to 2.5 g of average plant ash does not interfere. The final emission spectrometry of platinum was carried out in 15 A dc-arc at Pt I 265.942 nm in the presence of Au as internal standard (Au I 267.595 nm). RSD was 6.3% in average.