HPLC Coupled with ICP-MS

FIGURE 18.2 A typical configuration of an HPLC system interfaced with an ICP mass spectrometer (copyright 2003-2007, all rights reserved, PerkinElmer Inc.). 

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Ogra, Y. and Suzuki, K. T., Speciation of selenocompounds by capillary HPLC coupled with ICP-MS using multi-mode gel filtration columns. Journal of Analytical Atomic Spectrometry 20(1), 35-39, 2005. 

Extraction carried out with 1 mmol L Ca(NO3)2 aq, As species separated and detected using anion-exchange HPLC coupled with ICP-MS. 

Anion exchange chromatography coupled with ICP MS was used in the simultaneous speciation analysis of As, Se, Sb and Te compounds in extracts of fish [230]. Size exclusion chromatography (SEC) coupled with specific detectors is frequently used to analyse species of trace elements in protein-rich materials, such as extracts of meat and plant tissues. For instance, SEC hyphenated with ICP MS was used for the speciation analysis of Cu and Zn in samples of leguminous plants [191]. The same technique was applied to the speciation analysis of Cu, Cd, Zn, Se, As and Ca in fish [220] and Fe, Zn, Cu, Ag, Cd, Sn and Pb in mussels [189]. SEC HPLC coupled with GF AAS mmed out to be very useful for determining levels of Fe species in baby food [312]. With gel permeation chromatography (GPC) GF AAS, the speciation forms of Cd were determined in two kinds of vegetables contaminated with this element [216]. 

The presence of asymmetric carbons in selenomethionine, other a-selenoamino acids, and related compounds produces different chiral enantiomers with different physiological activities. HPLC separation of enantiomers is possible with a range of chiral stationary phases, d- and 1-Selenomethionine enantiomers have been resolved with an a-cyclodextrin stationary phase and other species with a teicoplanin-based chiral phase. Hybrid chiral methodologies based on GC, HPLC, and capillary electrophoresis, coupled with ICP-MS are feasible. Enantiomers of d,l-selenocystine, d,l-selenomethio-nine, and d,l-selenoethionine were examined in a range of commercial dietary supplements using a chiral crown ether stationary phase and ICP-MS detection. Selenium-em-iched onion, garlic, and yeast were analyzed and some of the selenoamino acid enantiomers were identified. l-Fluoro-2, 4-dinitro-phenyl-5-l-alanine amide was used to derivatize enantiomers of selenoamides for enhanced resolution. 

In the early days of coupling HPLC components with ICP-MS, there were very few sophisticated communication protocols between the two devices. The sample was injected into the chromatographic separation system, and when the analyte species was close to being eluted off the column, the read cycle of the ICP mass spectrometer was initiated manually to capture the data using the instrument s time-resolved software. Processing and manipulation of the data was then carried out after the chromatogram had been captured, sometimes by a completely different software... 

Microwave plasma detection has been reviewed [351], also in relation to GC [352,353], Coupling of chromatography (GC, SFC, HPLC) and capillary electrophoresis (CE) with ICP-MS and MIP-MS detectors has also been reviewed [181,334,335]. Various specific GC-ICP-MS reviews have appeared [334,337,345,346,354,355]. 

Evaporative LC-FTIR is rapidly gaining industrial acceptance as a useful tool in low-MW additive analysis. HPLC has also been coupled with various element-selective detectors. There is significant demand for speciation information for many elements, and the separation ability of chromatography coupled to ICP-MS offers the analyst a versatile tool for such studies. It is apparent that ICP-MS is increasingly being employed for chromatographic detection. Several modes of GC, SFC, LC and CE have been hyphenated with ICP-MS for improved detection limits compared to other traditional methods of detection such as UV-VIS spectroscopy. Inorganic speciation deserves more attention. 

Determination of iodo amino acids by HPLC with inductively coupled plasma (ICP)-MS detection had LOD 35-130 pg of I, which is about one order of magnitude lower than with UVD usually applied for these compounds175. Amino acids and peptides containing sulfur, such as cysteine, cystine, methionine and glutathione, can be determined after HPLC separation by pulsed electrochemical detection, using gold electrodes176. 

A direct injection nebuliser (DIN) was used to interface LC with ICP-MS (Shum et al., 1992a). The DIN transferred all of the sample into the inductively coupled plasma. Microscale LC separations in small packed columns were studied because the column flow rates of about 30 ml min 1 were compatible with the DIN. The low dead volume (less than 1 ml) of the interface prevented excessive band broadening. Eluents containing up to 85% methanol were accommodated. The analyte signal varied by about 20% as the eluent changed from 20% to 80% methanol in water. Detection limits for arsenic and tin species using the HPLC-DIN-ICP-MS system were 0.2-0.6 and 8-10pg, respectively. 

The separation component of the coupled system becomes of particular concern when the target species have similar physicalDchemical properties. GC should be chosen wherever possible because it offers a high separation efficiency and very low LoDs can be achieved because of the absence of the condensed mobile phase. For nonvolatile species liquid phase column separation techniques, such as HPLC and CE, are the usual choice. They can be easily coupled on-line with ICP-MS. A variety of separation mechanisms and mobile phases can be used to allow the species identity to be preserved. 

To study the abiotic formation of Me-Hg from Hg2+ as well as demethylation of Me-Hg to Hg2+ in biological tissues during treatment with TMAH, enriched isotope standards from Me198Hg and 201Hg2+ were added to the samples to monitor species transformation and to apply species-specific isotope dilution (SSID) calibration. The HPLC instrumental set-up with a C18 column and an aqueous phase eluent was directly coupled to ICP-MS [31]. 

In past years, on line chromatographic coupling techniques such as HPLC and CE coupled to ICP-MS with the isotope dilution technique have been used for element quantification in speciation analysis. An interesting application of the isotope dilution technique in medical research was proposed recently by Prange and co-workers, who added highly enriched " S, Cu, Zn and Cd spikes to the interface of the CE-ICP-MS system. The authors separated isoforms of metallothionein (e.g., of rabbit liver) by capillary electrophoresis and quantified S, Cd, Cu and Zn concentrations in isoforms by ICP-SFMS using the isotope dilution technique. A new selenized yeast reference material (SELM-1) for methionine, selenomethionine (SeMet) and total selenium content has also certified by an intercomparison exercise. ... 

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