HPLC/ICPMS

C.J. Duckett, J.C. Lindon, H. Walker, F. Abou-Shakra, I.D. Wilson, J.K. Nicholson, Metabolism of 3-chloro-4-fluoroaniline in rat using [C-14]-radiolabelling, F-19-NMR spectroscopy, HPLC-MS/MS, HPLC-ICPMS and HPLC-NMR, Xenobiotica 36 (2006) 59-77. 

Figure 16.4. HPLC-ICPMS chromatogram of oyster tissue (1) arsenite (2) unknown (3) MMADPQ-arsenosugar (4) DMA (5) S04-arsenosugar (6) arsenate (7), (8) and (9) unknown (10) OH-arsenosugar (11) unknown (12) arsenobetaine (13) TMAO (14) arsenocholine (15) TMAs (courtesy of Dr Ute Kohlmeyer, GALAB Laboratories, Geesthacht).

J. Ruiz Encinar, L. Ouerdane, W. Buchmann, J. Tortajada, R. -obin ski, J. Szpunar, Identibcation of water-soluble selenium-containing proteins in selenized yeast by size-exclusion-re versed-phase HPLC/ICPMS followed by MALDI-TOF and electrospray Q-TOF Mass Spectrometry, Anal. Chem., 75 (2003), 3765D3774. 

J. Edmonds, Y. Shibata, R. Francesconi, R. Rippinggale, M. Morita, Arsenic transformations in short marine food chains studied by HPLC-ICPMS, Appl. Organomet. Chem., 11 (1997), 281-287. 

K. T. Suzuki, K. Ishiwata, Y. Ogra, Incorporation of selenium into selenoprotein P and extracellular glutathione peroxidase HPLC-ICPMS data with enriched selenite, Analyst, 124 (1999), 1749D1753. 

Yathavakilla, S.K.V. and Caruso, J.A. Study of Se-Hg antagonism in Glycine max (soybean) roots by size exclusion and reversed phase HPLC-ICPMS. Anal. Bioanal. Chem. 2007, 389, 715-723. 

The concentrations of the three arsenicals (75-77) were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by high-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS) [170]. All three organoarsenics, which occurred at pg/kg concentrations, were detected in 25, 23 and 17 of the 37 samples analyzed, respectively. The limits of detection were 2-3 pg/kg dry mass. The data illustrate that all three compounds are common minor constituents in practically all marine samples. 

Analysis of 10 crude fish oils from various regions of the world for arsenolipids was performed by normal phase HPLC-ICPMS with various mixtures of organic solvents as mobile phases [172]. All ten fish oils appeared to contain the same 4-6 major arsenolipids, but in varying amounts depending on the origin of the fish. Further chromatography of some of the oils imder both normal phase and reversed-phase conditions indicated the presence of many more minor arsenolipids. Unfortunately, the authors did not provide any data on the structures of the arsenolipids they described. 

HPLC/ICPMS is a powerful analytical technique and is now the most commonly used method for determining selenium urinary metabolites [215]. Over the last 10 years, most of the reports of selenium species in urine have used HPLC/ICPMS, sometimes together with molecular MS techniques. In this period, a total of 16 selenium species (see below) have been reported in urine, most of them novel human metabolites and some of them completely new compounds. 

These 16 compounds identified in urine mostly by HPLC/ICPMS include the compound 102 plus 15 other selenium metabolites (Table 18). For many of these, the assignments have been made on very little evidence and require confirmation before the compounds can be accepted as typical urine metabolites [216, 217]. Some, such as methylselenol, have already been retracted by their discoverers. Selenosugar 95 is now firmly established as a major urinary metabolite when selenium is administered, and it is also a constituent of natural urine. There have also been reports of selenosugar 94 and selenosugar 96 as minor constituents. Selenite appears to be a common minor metabolite in normal urine. 

Selenocystamine (104) 1 Not yet the HPLC/ICPMS data do not match the MS/MS data... 

Ongoing investigations into selenium metabolism include state-of-the-art methods such as HPLC/ICPMS in combination with MS/MS. Data on the profile of selenium metabolites will elucidate the element s essential and toxic roles and relate individual Se species with observed health effects. 

As shown in Table 7.3, the results obtained for As, Cu, Mn and Zn are in good agreement with the certified values. In the case of As, determinations by HPLC/ICPMS have allowed to determine the respective amounts of As-species found after each treatment which were as follows ... 

The homogeneity was verified by repeated determinations of total As, arsenobetaine and DMA. The total As content was determined by HG-QFAAS after assisted digestion whereas DMA was determined by HPLC-ICPMS. No inhomogeneity was suspected at a level of 0.3 g for total As and I g for As-species, and the material was considered to be suitable for use as a CRM. 

Differences in standard deviations between two HPLC-ICPMS sets for tributyltin were due to the fact that the lower SD was obtained by an isotope-dilution methodology. 

Consequently, the RM 424 was not certified and was considered as a research material for laboratories willing to evaluate techniques such as e.g. GC/FPD, GC/MS or HPLC/ICPMS. The reference value (unweighted mean of 8 accepted sets of results) and its standard deviation is (20 5) pg kg as mass fractions (based on dry mass) of TBT cation. 

The dimethylarsinoyl derivative of sulfated ribitol (see Fig. 2, compound 15) was isolated from the red alga Chondria crassicaulis (38). It had been observed as a major arsenical in C. crassicaulis by high performance liquid chroma-tography-inductively coupled plasma mass spectrometry (HPLC-ICPMS), and was initially reported as an unknown because it did not match any available standard (39). Subsequently, the compound was isolated and a chemical structure was proposed chiefly on nuclear magnetic resonance (NMR) data chemical synthesis of authentic material confirmed the proposed structure (38). This com-... 

A trimethyiarsoniosugar (see Fig. 2, compound 13) was identified in three species of gastropods by HPLC-ICPMS (40). This compound is a trimethyiated anaiogue of one of the most common arsenosugars found in marine sampies. A trimethyiated anaiogue (see Fig. 2, compound 12) of another common arseno-sugar was eariier reported in aigae (41). 

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