Delta34S measurements of sulfur by multicollector inductively coupled plasma mass spectrometry.

An accurate and precise method for the determination of delta34S measurements by multicollector inductively coupled plasma mass spectrometry has been developed. Full uncertainty budgets, taking into consideration all the uncertainties of the measurement process, have been calculated. The technique was evaluated by comparing measured values with a range of isotopically enriched sulfur solutions prepared by gravimetric addition of a 34S spike. The gravimetric and measured results exhibited a correlation of R2 >0.999. Repeat measurements were also made after adding Na (up to 420 microg g(-1)) and Ca (up to 400 microg g(-1)) salts to the sulfur standard. No significant deviations in the delta34S values were observed. The Russell correction expression (Ingle, C.; Sharp, B.; Horstwood, M.; Parrish, R.; Lewis, D. J. J. Anal. At. Spectrom. 2003, 18, 219) was used to correct for mass bias on the 34S/32S isotope amount ratio from the mass bias observed for the 30Si/28Si isotope amount ratio. Consistent compensation for instrumental mass bias was achieved. Resolution of the measured delta34S values was better than 1 per thousand after consideration of all uncertainty components. The technique was evaluated for practical applications by measurement of delta34S for a range of mineral waters by pneumatic nebulization sample introduction and the analysis of genuine and counterfeit pharmaceuticals using both laser ablation sample introduction and liquid chromatography. For the former two cases polyatomic interferences were resolved by operating the MC-ICPMS in medium resolution, while for the chromatographic analyses polyatomic interferences were minimized by the use of a membrane desolvator, allowing the instrument to be operated at a resolution of 400.

Current mass spectrometry strategies for selenium speciation in dietary sources of high-selenium.

This document reviews the most relevant mass spectrometry approaches to selenium (Se) speciation in high-Se food supplements in terms of qualitative and quantitative Se speciation and Se-containing species identification, with special reference to high-Se yeast, garlic, onions and Brazil nuts. Important topics such as complexity of Se speciation in these materials and the importance of combining Se-specific detection and molecule-specific determination of the particular species of this element in parallel with chromatography, to understand their nutritional role and cancer preventive properties are critically discussed throughout. The versatility and potential of mass spectrometric detection in this field are clearly demonstrated. Although great advances have been achieved, further developments are required, especially if "speciated"certified reference materials (CRMs) are to be produced for validation of measurements of target Se-containing species in Se-food supplements.

A comparison of double-focusing sector field ICP-MS, ICP-OES and octopole collision cell ICP-MS for the high-accuracy determination of calcium in human serum.

Human serum is routinely measured for total calcium content in clinical studies. A definitive high-accuracy and low-uncertainty method is required for reference measurements to underpin medical diagnoses. This study presents a novel octopole collision cell ICP-MS, high-accuracy, methodology and comparison of that technique with double-focusing sector field ICP-MS and an ICP-OES method. Double-matched isotope dilution mass spectrometry (IDMS) was employed for ICP-MS techniques and an exact matching bracketing technique using scandium as an internal standard was used for ICP-OES analysis. Medium resolution mode was utilised for double-focusing sector field ICP-MS analysis to resolve the dominant interferences on the (44)Ca/(42)Ca isotope pair. Hydrogen reaction gas was employed to chemically resolve a number of polyatomic interferences predominantly through charge transfer reactions in the octopole collision cell. Comparison data presented for NIST CRM 909b human serum analysis from all three techniques demonstrates highest accuracy (99.6%) and lowest uncertainty (1.1%) for octopole collision cell ICP-MS. Data from ICP-OES using a non-IDMS technique produces comparably accurate data and low-uncertainties. The much higher total expanded uncertainties for double-focusing sector field ICP-MS compared with octopole collision cell data are explained by lower precision on the measurement of the (44)Ca/(42)Ca isotope ratio. Data for octopole collision cell ICP-MS submitted for an international blind trial comparison (CCQM K-14) demonstrated excellent agreement with the mean of all participants with a low expanded uncertainty.

Simultaneous co-extraction of organometallic species of different elements by accelerated solvent extraction and analysis by inductively coupled plasma mass spectrometry coupled to liquid and gas chromatography.

This paper describes the development of an accelerated solvent extraction methodology that is capable of simultaneously extracting organometallic species of As, Sn and Hg in a semi-automated manner. Accelerated solvent extraction (ASE) methods based on previous research on the separate extraction of organotin and -arsenic species in our laboratory were adapted for the co-extraction of six different species from an oyster tissue certified reference material (BCR 710). For the first time, the extraction of MeHg by this technique is also investigated. The proposed ASE conditions employed 50% acetic acid in methanol at a temperature of 100 degrees C with up to five consecutive extraction cycles of 3 minutes. Extraction efficiencies for organoarsenic species ranged from 80% (dimethylarsinic acid, DMA) to 99% for arsenobetaine (AsB). Species of toxicological interest, such as dibutyltin (DBT), tributyltin (TBT) and methylmercury (MeHg), were extracted with mean recoveries of 81, 84 and 76%, respectively. The extracted species were analysed by gas chromatography/inductively coupled plasma mass spectrometry (GC/ICPMS; DBT, TBT and MeHg) and liquid chromatography/inductively coupled plasma mass spectrometry (LC/ICPMS; MMA, DMA, AsB) after ethylation with sodium tetraethylborate or dilution with water, respectively. In addition to those species for which the extraction efficiency was assessed during this study, a further five arsenic species (arsenite, arsenate and three unidentified species), as well as monobutyltin (MBT) and mono-, di- and triphenyltin, could also be extracted from other matrices. The developed ASE method provides a significant improvement over many currently available routine monitoring methods for trace element speciation due to the fact that it is capable of extracting several species of toxicological interest simultaneously and quantitatively.

Comparison of different liquid chromatography conditions for the separation and analysis of organotin compounds in mussel and oyster tissue by liquid chromatography-inductively coupled plasma mass spectrometry.

In this paper, a new high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) methodology for the analysis of organotin compounds in complex matrices is described. Earlier studies had failed to show baseline resolution between dibutyltin (DBT) and triphenyltin (TPhT). The data presented in this paper show that, by using a different C-18 stationary phase material (Ace C-18) with decreased particle size, baseline resolution of DBT and TPhT can be achieved, with the resultant separation of a third interfering component. In addition, the Ace C-18 stationary phase yields a significant increase in the number of theoretical plates, and, combined with changes in the mobile phase composition, a reduction in run-time by approximately 25%. It is shown that the minor compounds detected are present in the sample and not artefacts of the analytical procedure. The accuracy and precision of the proposed HPLC-ICP-MS method was demonstrated for the determination of TBT in oyster tissue during the BCR "MULSPOT" international interlaboratory certification project.

Quantitation of oligonucleotides by phosphodiesterase digestion followed by isotope dilution mass spectrometry: proof of concept.

The importance of DNA as a regulatory analyte is well-known. Recent years have seen an increased interest in the quantitation of this analyte. Accurate quantitative measurements have been hampered by the lack of well-characterized standards and pure materials for this large-molecular-weight analyte. Outlined here is an approach for the accurate and reproducible quantitation of an oligonucleotide that is solely reliant on the availability of pure, well-characterized deoxynucleotides and not a sequence-specific pure DNA standard. The proposed procedure is intended to provide an accurate and definitive method for the quantitation of DNA for reference measurements as an improved alternative to the more conventional UV absorbance-based methods. For proof of concept, a gravimetrically prepared oligonucleotide solution was enzymatically digested to its constituent monomer-deoxynucleotide monophosphates (dNMPs), of which there are four different types. Qualitative mass spectrometry was used to confirm the 100% successful completion of the enzymatic digestion step. The dNMPs were then separated by liquid chromatography (LC) before being detected by electrospray ionization (ESI) mass spectrometry (MS). The method of quantitation was based on isotope dilution mass spectrometry (IDMS) analysis of the four different monomer units. The concentrations of the four dNMP residues were then summed to obtain the original concentration of the oligonucleotide. The concentrations determined by liquid chromatography/mass spectrometry (LC/MS) and also by liquid chromatography-tandem mass spectrometry (LC/MS/MS) differed by <2.5 and 1%, respectively, from the gravimetrically assigned value. These differences were well within the uncertainty of the gravimetrically assigned value. This highly accurate method, suitable for the definitive quantitation of oligonucleotides, should be ideal for characterizing primary calibration standards and certified reference materials that can then be used to underpin the more conventional quantitative techniques of UV and fluorescence spectroscopy.