Mass Spectrometry Combined with Inductively Coupled Plasma

7 Mass Spectrometry Combined with Inductively Coupled Plasma 

Personnel working in some programs at the Los Alamos National Laboratory (LANL) may handle radioactive materials that, under certain circumstances, could be taken into the body. Employees are monitored for such intakes through a series of routine and special bioassay measurements. One such measurement involves a thermal ionization mass spectrometer. In this technique, the metals in a sample are electroplated onto a rhenium filament. This filament is inserted into the ion source of the mass spectrometer and a current is passed through it. The ions of the plutonium isotopes are thus formed and then accelerated through the magnetic held. The number of ions of each isotope are counted and the amount of Pu-239 in the original sample calculated by comparison to a standard. 

Kim Israel, a technician at LANL, Chemistry Division Bioassay Program, runs a thermal ionization mass spectrometry (TIMS) instrument. 

FIGURE 10.20 An illustration of a mass spectrometer coupled to an inductively coupled plasma instrument. 

The analysis of tetramethylammonium hydroxide (TMAH) solutions manufactured by SACHEM Inc. of Cleburne, Texas, includes the determination of trace elements. These elements cause less-than-optimum performance of integrated circuit boards manufactured by SACHEM s customers that use these solutions in their processes. Alkali and alkaline earth metals (e.g., Li, Na, K, Mg, Ca, and Ba) can reduce the oxide breakdown voltage of the devices. In addition, transition and heavy metal elements (e.g., Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Au, and Pb) can produce higher dark current. Doping elements (e.g., B, Al, Si, P, As, and Sn) can alter the operating characteristics of the devices. In SACHEM s quality control laboratory, ICP coupled to mass spectrometry is used to simultaneously analyze multiple trace elements in one sample in just 1 to 4 min. This ICP-MS instrument is a state-of-the-art instrument that can provide high throughput and low detection Emits at the parts per thousand level. Trace elemental determination at the parts per thousand level must be performed in a clean room so that trace elemental contamination from airborne particles can be minimized. 

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Laser based mass spectrometric methods, such as laser ionization (LIMS) and laser ablation in combination with inductively coupled plasma mass spectrometry (LA-ICP-MS) are powerful analytical techniques for survey analysis of solid substances. To realize the analytical performances methods for the direct trace analysis of synthetic and natural crystals modification of a traditional analytical technique was necessary and suitable standard reference materials (SRM) were required. Recent developments allowed extending the range of analytical applications of LIMS and LA-ICP-MS will be presented and discussed. For example ... 

Moens, L., DeSmaele, T., Dams, R., VandenBroeck, R and Sandra, P. (1997) Sensitive, simultaneous determination of organomercury, -lead, and -tin compounds with headspace solid phase microextraction capillary gas chromatography combined with inductively coupled plasma mass spectrometry. Anal. Chem., 69, 1604—1611. 

Shkinev, VM., Fedorova, O.M., Spivakov, B.Ya., Mattusch, J., Wennrich, R. and Lohse, M. (1996) Speciation of metals associated with natural water components by on-line membrane fractionation combined with inductively coupled plasma atomic emission and mass spectrometries. Anal. Chim. Acta, 327, 167-174. 

K. E. 0degard, W. Lund, Multi-element speciation of tea infusion using cation-exchange separation and size-exclusion chromatography in combination with inductively coupled plasma mass spectrometry, J. Anal. Atom Spectrom., 12 (1997), 403-408. 

It has been shown that the major part of Ca and Mg are found in the soluble fraction (whey) of human milk, whereas only small amounts are present in insoluble caseins or in fat [11-13]. Calcium and Mg speciation studies in milk whey using size exclusion chromatography (SEC) combined with inductively coupled plasma atomic emission spectrometry (ICP-AES) [14] indicated that they were preferably associated with the milk nonprotein fraction. A further work [15] showed similar chromatographic profiles by SEC hyphenated with inductively coupled plasma mass spectrometry (ICP-MS), with Ca and Mg eluting in the lowmolecular-weight region (LMW) (<1.4 kDa). Thus, there seem to be weak associations, if any, of Ca2+ or Mg2+ with higher molecular mass biocompounds of milk. 

S. McSheehy, Z. Mester, Arsenic speciation in marine certified reference materials. Part 1. Identification of water-soluble arsenic species using multidimensional liquid chromatography combined with inductively coupled plasma, electrospray and electrospray high-field asymmetric waveform ion mobility spectrometry with mass spectro-metric detection, J. Anal. Atom. Spectrom., 19 (2004), 373-380. 

Nakazato, T., Tao, H., Taniguchi, T., Isshiki, K. Determination of arsenite, arsenate, and monomethylarsonic acid in seawater by ion-exclusion chromatography combined with inductively coupled plasma mass spectrometry using reaction cell and hydride generation techniques. Talanta 58, 121-132 (2002)... 

Zhou F (1996) Stripping analysis combined on-line with inductively coupled plasma-atomic emission spectrometry and with inductively coupled plasma-mass spectrometry. Electroanalysis 8 855-... 

J. Yin, Z. Jiang, G. Chang, and B. Hu. Simultaneous on-line preconcentration and determination of trace metals in environmental samples by flow injection combined with inductively coupled plasma mass spectrometry using a nanometer-sized alumina packed micro-column. Analytica Chimica Acta 540 333-339, 2005. 

Benkhedda K., Dimitrova B., Infante H. G., Ivanova E. and Adams F. C. (2003) Simultaneous on-line preconcentration and determination of Pt, Rh and Pd in urine, serum and road dust by flow injection combined with inductively coupled plasma time-of-flight mass spectrometry, J. Anal. At. Spectrom. 18 1019-1025. 

Hioki, A., Lam,J.W. H., and McLaren, J.W. (1997). On-line determination of dissolved silica in seawater by ion exclusion chromatography in combination with inductively coupled plasma mass spectrometry. Anal. Chem. 69(1), 21. 

Inoue Y, Kawabata K (1993) Speciation of organotin compounds by inductively coupled plasma mass spectrometry combined with liquid chromatography. Journal of the Mass Spectrometry Society of Japan, 41 (4) 245-251. 

The most frequently applied analytical methods used for characterizing bulk and layered systems (wafers and layers for microelectronics see the example in the schematic on the right-hand side) are summarized in Figure 9.4. Besides mass spectrometric techniques there are a multitude of alternative powerful analytical techniques for characterizing such multi-layered systems. The analytical methods used for determining trace and ultratrace elements in, for example, high purity materials for microelectronic applications include AAS (atomic absorption spectrometry), XRF (X-ray fluorescence analysis), ICP-OES (optical emission spectroscopy with inductively coupled plasma), NAA (neutron activation analysis) and others. For the characterization of layered systems or for the determination of surface contamination, XPS (X-ray photon electron spectroscopy), SEM-EDX (secondary electron microscopy combined with energy disperse X-ray analysis) and... 

The quasi-simultaneous separation and determination of lanthanides and actinides by ion chromatography inductively coupled plasma mass spectrometry combined with the isotope dilution technique and the further use of ion chromatography for the determination of fission products and actinides in nuclear applications are described by Betti et ul.10 48 68... 

S. Yali, G. Xiyun, D. Andao, Determination of platinum group elements by inductively coupled plasma-mass spectrometry combined with nickel sulphide E>re assay and tellurium coprecipitation, Spectrochim. Acta, 53B (1998), 1463D1467. 

Shazali 1, Van t Dack L, Gijbels R (1987) Determination of precious metals in ores and rocks by thermal neutron activation/y-spectrometry after preconcentration by nickel sulfide fire assay and coprecipitation with tellurium. Anal Chim Acta 196 49-58 Stembeck J, Sjodin A, Andreasson K (2002) Metal emissions from road traffic and the influence of resuspension—results from two tunnel studies. Atmos Env 36 4735-4744 Sun Y, Guan X, Du A (1998) Determination of platinum group elements by inductively coupled plasma-mass spectrometry combined with nickel sulfide fire assay and tellurium coprecipitation. Spectrochim Acta B 53 1463-1467... 

SchaumlofFel, D., and Prange, A. (1999). A new interface for combining capillary electrophoresis with inductively coupled plasma-mass spectrometry. Fresenius J. Anal. Chem. 364(5), 452. 

Vijayalakshmi, S., Prabhu, R. K., Mahalingam.T. R., and Mathews, C. K. (1992). Determination of trace metals in uranium oxide by inductively coupled plasma mass spectrometry combined with on-line solvent extraction.J. Anal. At. Spectrom. 7(3), 565. 

Chudzinska, M. and Baralkiewicz, D. (2010). Estimation of honey authenticity by multielements characteristics using inductively coupled plasma-mass spectrometry (ICP-MS) combined with chemometrics. Food Chem. Toxicol. 48, 284-290. 

Multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) combines sector-field ICPMS with a multiple collector detector system and has recently emerged as an alternative to TIMS for precise U-Th isotope measurement. The full potential of MC-ICPMS has yet to be realized. Yet despite this, its performance in high precision isotope measurement already challenges and, in some cases, surpasses that ever achieved by TIMS (e.g., Lee and Halliday 1995 Blichert-Toft and Albarede 1997). 

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