Simultaneous multi-elemental speciation analysis of organometallic compounds by solid-phase microextraction and multicapillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight-mass spectrometry
07 Jul 2004-Journal of Analytical Atomic Spectrometry (The Royal Society of Chemistry)-Vol. 19, Iss: 7, pp 867-875
TL;DR: In this paper, a simple, rapid and accurate method on the basis of solid phase microextraction (SPME) in combination with multicapillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS) was developed for simultaneous speciation analysis of 10 organometallic compounds of mercury (including inorganic mercury), tin and lead.
Abstract: A simple, rapid and accurate method on the basis of solid phase microextraction (SPME) in combination with multicapillary gas chromatography (MCGC) hyphenated to inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS) was developed for simultaneous speciation analysis of 10 organometallic compounds of mercury (including inorganic mercury), tin and lead. Headspace SPME was used for extraction/preconcentration of the species from the sample after derivatization with sodium tetraethylborate and subsequent volatilization. Seven SPME fibers were compared in terms of extraction efficiency. A 65 µm polydimethylsiloxane/divinylbenzene fiber offered the best overall extraction efficiency. Using MCGC separation, a total chromatographic run time below 200 s was obtained. With ICP-TOFMS detection peak widths at half height (FWHM) down to 0.3 s were measured without spectral skew thanks to the simultaneous character of the mass spectrometer. Detection limits well below pg g−1 levels were obtained for trimethyllead (TML), dimethyllead (DML), trimethyltin (TMT), dimethyltin (DMT), monomethyltin (MMT), monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT). Somewhat higher detection limits were obtained for methylmercury (MeHg, 1.3 pg g−1) and inorganic mercury (Hg2+, 2.0 pg g−1). For extraction/preconcentration of MeHg and Hg2+ the 75 µm carboxen/polydimethylsiloxane (CAR/PDMS) fiber is a better choice. The analytical precision (RSD, %) for 10 successive injections of a standard mixture containing 100 pg of each species was generally below 5%. Propylmercury (PrHg) was used as the internal standard for MeHg and Hg2+ as well as for lead species determination. The method was validated by the analysis of biological and road dust certified reference materials (CRMs).
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4,485 citations
TL;DR: In this article, a modification of the solid-phase microextraction method (SPME) is proposed to shortens the time of extraction and facilitates the application of this method to analysis of solid samples.
Abstract: Headspace solid-phase microextraction is a solvent-free sample preparation technique in which a fused silica fiber coated with polymeric organic liquid is introduced into the headspace above the sample. The volatilized organic analytes are extracted and concentrated in the coating and then transferred to the analytical instrument for desorption and analysis. This modification of the solid-phase microextraction method (SPME) shortens the time of extraction and facilitates the application of this method to analysis of solid samples. The detection limits of the headspace SPME technique are at ppt level when ion trap mass spectrometry is used as the detector and are very similar to that of the direct SPME technique
1,157 citations
TL;DR: The objective of this perspective is to summarize the fundamental aspects of sample preparation and anticipate future developments and research needs.
Abstract: The sample preparation step in an analytical process typically consists of an extraction procedure that results in the isolation and enrichment of components of interest from a sample matrix. Extraction can vary in degree of selectivity, speed, and convenience and depends not only on the approach and conditions used but on the geometric configurations of the extraction phase. Increased interest in sample preparation research has been generated by the introduction of nontraditional extraction technologies. These technologies address the need for reduction of solvent use, automation, and miniaturization and ultimately lead to on-site in situ and in vivo implementation. These extraction approaches are frequently easier to operate but provide optimization challenges. More fundamental knowledge is required by an analytical chemist not only about equilibrium conditions but, more importantly, about the kinetics of mass transfer in the extraction systems. Optimization of this extraction process enhances overall a...
257 citations
TL;DR: The use of solid phase microextraction (SPME) technique for the simultaneous determination of organomercury, -tin, and -lead is described in this paper, where the organometallic compounds were in situ derivatized with sodium tetraethylborate, sorbed on a poly(dimethylsiloxane)-coated fused silica fiber and desorbed in the splitless injection port of the GC.
Abstract: The use of the solid phase microextraction (SPME) technique for the simultaneous determination of organomercury, -tin, and -lead is described. The organometallic compounds were in situ derivatized with sodium tetraethylborate, sorbed on a poly(dimethylsiloxane)-coated fused silica fiber, and desorbed in the splitless injection port of the GC. The different organometallic compounds were simultaneously determined by an inductively coupled plasma mass spectrometer (ICPMS) coupled to the GC using a transfer line developed in-house. The detection limits obtained with CGC−ICPMS for monobutyl-, dibutyl-, and tributyltin are between 0.34 and 2.1 ng/L as Sn. Analysis of a PACS-1 reference material confirmed the reliability of the combination of SPME as extraction technique with CGC−ICPMS for the analysis of organotin compounds.
192 citations
TL;DR: In this paper, a theoretical treatment of the headspace SPME process is proposed, focusing on the mass transfer at the two interfaces, condensed phase/gas phase and gas phase/SPME polymer.
Abstract: Solid phase microextraction (SPME) has remarkable advantages in headspace chemical analysis over conventional static headspace and purge-and-trap techniques in terms of its ease of use and superior reproducibility. A theoretical treatment of the headspace SPME process is proposed in this report that focuses on the mass transfer at the two interfaces, condensed phase/gas phase and gas phase/SPME polymer. The rate-determining step of the SPME process can be either the analyte evaporation from the condensed phase to its headspace or the analyte diffusion from the SPME polymer film surface into its inner layers. Mass transfer in the gas phase is considered a fast process. The mathematical solution provides an expression that correlates the amount of extracted analyte with its initial concentration in the condensed phase. A directly proportional relationship exists between them in all cases of headspace SPME, and this relationship indicates that SPME quantification is feasible before reaching a partition equil...
158 citations