Mass spectrometry organotin compounds

Inductively coupled plasma mass spectrometry was applied to the analysis of six organotin compounds (chlorides of dimethyl-, dibutyl-, trimethyl-, tributyl-, diphenyl-, and triphenyltin). Detection hmits for the six organotins ranged from 24 to 51 pg as tin the dynamic range was over lO, from 1 pg/1 to 10 mg/1 (Inoue Kawabata, 1993). 

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. 

There are still rather few fundamental studies of the mass spectrometry of organotin compounds, but the fragmentation pathways of organotin compounds have been further elucidated by means of tandem mass spectrometry.51,52... 

Inoue, Y., Kawabata, K. and Suzuki, Y. (1995) Speciation of organotin compounds using inductively-coupled plasma-mass spectrometry with micellar liquid-chromatography. J. Anal. At. Spectrom., 10, 363-266. 

Suyani, H., Creed, J., Caruso, J. and Satzger, R.D. (1989) Helium microwave-induced plasma mass spectrometry for capillary gas chromatographic detection speciation of organotin compounds./. Anal. At. Spectrom., 4, 777-782. 

The impact of several factors on the MMLLE extraction yield of PAHs in water has been comprehensively studied using a flowing FS-MMLLE system and off-line analysis with GC-flame ionization detection (GC-FID).84 The flowing FS-MMLLE procedure combined with off-line GC-mass spectrometry (GC-MS) analysis has been utilized for the extraction of nonionic and derivatized ionic organotin compounds in river water.85... 

Ndungu, K. and L. Mathiasson. 2000. Microporous membrane liquid-liquid extraction technique combined with gas chromatography mass spectrometry for the determination of organotin compounds. Anal. Chim. Acta 404 319-328. 

Rosenberg, E., V. Kmetov, and M. Grasserbauer. 2000. Investigating the potential of high-performance liquid chromatography with atmospheric pressure chemical ionization-mass spectrometry as an alternative method for the speciation analysis of organotin compounds. Fresenius J. Anal. Chem. 366 400-407. 

White, S., T. Catterick, B. Fairman, et al. 1998. Speciation of organotin compounds using liquid chromatography-atmospheric pressure ionisation mass spectrometry and liquid chromatography-inductively coupled plasma mass spectrometry as complementary techniques. J. Chromatogr. A 794 211-218. 

Shen et al. [262] evaluated indirectly coupled plasma mass spectrometry as an element detector for the supercritical fluid chromatography of organotin compounds in water. Detection limits of 0.04 and 0.047pg absolute were obtained, respectively, for tetrabutyltin and tetraphenyltin. 

Unger et al. [217] determined butyltins in non saline water by gas chromatography with flame photometric detection and confirmation by mass spectrometry. The sample was extracted with tropalone in //-hexane and organotin compounds derivatised with n-hexyl magnesium bromide to form tetraalkyltins. The n-hexyl derivatives of methyltin and butyltin species were easily separated and quantified relative to an internal standard (triphenyltin chloride) which was not found to be present in environmental samples and did not interfere. 

Plzak ei al. [220] extracted organotin compounds into hexane and derivitivised by methylation with a Grignard reagent or reduced to tin hydride with sodium borohydride prior to determination by gas chromatography-mass spectrometry. 

Low-pressure He-ICPs have been used as chromatographic detectors for mass spectrometry [111,112,114], Organotin compounds [112] were speciated by using a plasma operated at 100 W. A low-pressure torch must be constructed from a quartz tube of dimensions approximately 150 mm long and 6 mm outer diameter to sustain such a plasma. This torch is connected at one end to the GC interface and to the sampler cone at the other. Heated transfer lines must be used for reproducible transfer of the GC analytes. As the low-pressure system may not completely at-... 

Organotin compounds, as well as being open to study by general spectroscopic techniques, e.g. UV, IR, and H and NMR spectroscopies as well as mass spectrometry, can also be investigated using such specific techniques as " Sn (or " Sn) NMR and " Sn Mdssbauer spectroscopies. The increasing availability of solid-state NMR spectroscopy provides further means of exploring stractures. 

Rather limited use has been made of mass spectrometry in the study of organotin compounds,23-24 though MS linked to gas-liquid chromatography is now being used for the identification of organotin compounds, particularly in environmental studies. Most of the early work involved electron ionisation (El), but in recent years, other techniques such as chemical ionisation (Cl),25 fast atom bombardment (FAB),26, 27 field desorption,28 surface ionisation,29 and, particularly, electrospray (ES),30 31 have been used. 

The organotin compounds R SnX are extracted then converted into the hydrides R SnH4 with NaBH4, or, more usually, are alkylated to R SnR 4 with a Grignard reagent or with NaBEt4. These volatile, relatively non-polar, compounds are then separated by GLC or HPLC and analysed by techniques such as atomic absorption, flame photometry, or mass spectrometry.43 45 At the moment GLC-FP or GLC-MS appear to give the best performance, but of the four steps that are involved in the analysis, namely extraction, derivatisation, separation, and detection, it is not the analysis itself, but rather the extraction and derivatisation that are the major source of errors and are most in need of improvement. 

Pseudo-Phase or Micellar LC is obtained by using an aqueous micellar solution which contains a svuTactant as the mobile phase. The stationary phase is bonded and non-polar, hence reverse-phase separation occurs. The mobile phase is conferred special properties and allows unique selectivity. The technique is inexpensive and produces low amounts of toxics since small volumes of organic solvents are required. The amounts of solvent are small enough that miceUar chromatography can be coupled with Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) for the detection of organotin compounds [31]. Further information is available in an earlier review on this specific topic [32]. 

Vercauteren, J., Peres, C., Devos, C., Sandra, P., Vanhaecke, F., and Moens, L., Stir-bar sorptive extraction for the determination of ppq-level traces of organotin compounds in environmental samples with thermal desorption-capillary gas chromatography-ICP mass spectrometry. Anal. Chem., 73, 1509-1514, 2001. 

Quite recently, mass spectrometry is emerging for analysis of organotin compounds in various matrices sediments, water, biological samples and sewage sludge (Table 20.4). 

Gui-Bin j, Qun-Fang Z and Bin H (2000) Speciation of organotin compounds, total tin, and major trace metal elements in poisoned human organs by gas chromatography-flame photometric detector and inductively coupled plasma mass spectrometry. Environ Sci Technol 34 2697-2702. 

The SFC separations that have been developed deal with a limited number of organotin compounds compared to HPLC or GC separations. The majority of SFC methods have been used to determine the tri- and tetrasubstituted butyl- and phenyltin compounds. Atmospheric pressure ionization tandem mass spectrometry has been used for the quantitation of TBT. The method relied on molecular fragmentation and tandem mass spectrometry for the... 

Organotin compounds have also been determined in house dust (Fromme et al. 2005) (see Table 3). Ultrasound-assisted extraction (USAE) was conducted with ethanol, followed by derivatization with sodium tetraethylborate (STEB) and liquid-liquid extraction with n-hexane. Extracts were analysed by gas chroma-tography/mass spectrometry. Recoveries higher than 70% and average LODs of 10 ng g were obtained. 

Hoppner and Zoepfl and Wowk and Dogiovanni have described gas chromatographic procedures for the separation of mixtures of tetraalkyltin and other organotin compounds. Umilin and Tsinvoi used the gas chromatography and mass spectrometry to investigate impurities such as tributyltinchloride in tetrabutyltin. 

Rivas C, Ebdon L, Hill SJ. Effect of different spray chambers on the determination of organotin compounds by high-performance liquid chromatography—inductively coupled plasma mass spectrometry. J Anal At Spec 1996 11 1147—50. 

Rivas, C., Ebdon, L., Evans, E. H., and Hill, S. J. (1996). An evaluation of reversed-phase and ion-exchange chromatography for use with inductively coupled plasma-mass spectrometry for the determination of organotin compounds. Appl. Organomet. Chem. 10(1), 61. 

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