Zoltán Mester

Review of applications of high-field asymmetric waveform ion mobility spectrometry (FAIMS) and differential mobility spectrometry (DMS)

High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) and Differential Mobility Spectrometry (DMS) harness differences in ion mobility in low and high electric fields to achieve a gas-phase separation of ions at atmospheric pressure. This separation is orthogonal to either chromatographic or mass spectrometric separation, thereby increasing the selectivity and specificity of analysis. The orthogonality of separation, which in some cases may obviate chromatographic separation, can be used to differentiate isomers, to reduce background, to resolve isobaric species, and to improve signal-to-noise ratios by selective ion transmission. This review will focus on the applications of these techniques to the separation of various classes of analytes, including chemical weapons, explosives, biologically active molecules, pharmaceuticals and pollutants. These papers cover the period up to January 2007.

Solid phase microextraction as a tool for trace element speciation

Abstract Applications of solid phase microextraction (SPME) for trace element speciation are reviewed. Because of the relative novelty of the technique in the inorganic analytical field, the first part of this review provides a short overview of the principles of SPME operation; the second part describes typical SPME applications to elemental speciation. Volatile organometallic compounds can be collected by SPME from the sample headspace or liquid phase, directly or after derivatization. The usual separation method for the collected volatile species is gas chromatography. Non-volatile analyte species can be collected from the sample liquid phase and separated by liquid chromatography or capillary electrophoresis. Currently, most SPME applications in the inorganic field comprise analyte ethylation and headspace extraction followed by gas chromatographic separation of tin, lead and mercury species. The use of SPME for the study of equilibria in complex systems is also discussed and future roles of solid phase microextraction in the inorganic analytical field are raised.

Headspace single-drop microextration for the detection of organotin compounds

The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid-liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM).

Speciation of organoarsenic compounds by polypyrrole-coated capillary in-tube solid phase microextraction coupled with liquid chromatography/electrospray ionization mass spectrometry

In-tube solid phase microextraction (SPME) is an on-line extraction technique for compounds in aqueous samples, in which analytes are extracted and concentrated from the sample directly into a coated capillary by repeated aspirate/dispense steps. In this paper, a polypyrrole (PPY) coated capillary and several commercially available capillaries (used for GC separation) were used to examine their extraction efficiencies to the organoarsenic compounds studied. Compared with commercial capillaries that were currently used for in-tube SPME, the PPY coated capillary has shown better extraction efficiency to most of the compounds studied, especially to the anionic species, due to the inherent multi-functionality of pyrrole polymer. For the first time, this PPY coated capillary has been used for automated in-tube SPME and speciation of organoarsenic species in aqueous samples when coupled with liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS). Organoarsenic compounds in water samples and arsenobetaine in a certified reference material (DORM-2) were analyzed by this method.

Determination of methylmercury in fish tissues by isotope dilution SPME-GC-ICP-MS

A method is described for the accurate and precise determination of monomethylmercury (MMHg) by species specific isotope dilution (ID) calibration using solid phase microextraction (SPME) in combination with gas chromatographic (GC) separation and inductively coupled plasma mass spectrometric (ICP-MS) detection. Samples were digested with methanolic potassium hydroxide, derivatized in aqueous solution with sodium tetrapropylborate and headspace sampled with a polydimethylsiloxane coated SPME fused silica fiber. The analyte was then directly transferred from the fiber to the head of the GC column for desorption by insertion of the fiber through the heated injection port. Reverse spike ID analysis was performed to determine the accurate concentration of an in-house synthesized 198Hg-enriched monomethylmercury (MM198Hg) spike [candidate Certified Reference Material (CRM) EOM-1] using two natural abundance MMHg standards. Concentrations of 0.719 ± 0.015 and 4.484 ± 0.029 µg g−1 (one standard deviation, n = 4) as Hg were obtained for MMHg in NRCC CRMs DOLT-2 and DORM-2, respectively, using the present method. These are in good agreement with the certified values of 0.693 ± 0.053 and 4.47 ± 0.32 µg g−1 (as 95% confidence interval). A MMHg concentration of 4.69 ± 0.12 µg g−1 (one standard deviation, n = 4) as Hg in DORM-2 was subsequently determined by standard additions calibration using ethylmercury (EtHg) as an internal standard. A nearly 4-fold improvement in the precision of determination using ID was obtained, clearly demonstrating its superiority in providing more precise results compared to the method of standard additions. The method was applied to the determination of MMHg in a new biological CRM DOLT-3 and a concentration of 1.540 ± 0.025 µg g−1 (one standard deviation, n = 6) as Hg was obtained. A method detection limit (3σ) of 2.1 ng g−1 was estimated for a 0.25 g of subsample, sufficiently low for the routine determination of MMHg in most biological samples.

Paradigms in isotope dilution mass spectrometry for elemental speciation analysis

Isotope dilution mass spectrometry currently stands out as the method providing results with unchallenged precision and accuracy in elemental speciation. However, recent history of isotope dilution mass spectrometry has shown that the extent to which this primary ratio measurement method can deliver accurate results is still subject of active research. In this review, we will summarize the fundamental prerequisites behind isotope dilution mass spectrometry and discuss their practical limits of validity and effects on the accuracy of the obtained results. This review is not to be viewed as a critique of isotope dilution; rather its purpose is to highlight the lesser studied aspects that will ensure and elevate current supremacy of the results obtained from this method.

Transmission X-ray microscopy for full-field nano-imaging of biomaterials

Imaging of cellular structure and extended tissue in biological materials requires nanometer resolution and good sample penetration, which can be provided by current full‐field transmission X‐ray microscopic techniques in the soft and hard X‐ray regions. The various capabilities of full‐field transmission X‐ray microscopy (TXM) include 3D tomography, Zernike phase contrast, quantification of absorption, and chemical identification via X‐ray fluorescence and X‐ray absorption near edge structure imaging. These techniques are discussed and compared in light of results from the imaging of biological materials including microorganisms, bone and mineralized tissue, and plants, with a focus on hard X‐ray TXM at ≤ 40‐nm resolution. Microsc. Res. Tech., 2011.

Application of isotope dilution to the determination of methylmercury in fish tissue by solid-phase microextraction gas chromatography-mass spectrometry

Species-specific isotope dilution (ID) calibration using solid-phase microextraction (SPME) in combination with gas chromatography-mass spectrometry (GC-MS) for separation and detection of methylmercury (MeHg) in fish tissue is described. Samples were digested with methanolic potassium hydroxide. Analytes were propylated and headspace sampled with a polydimethylsiloxane-coated SPME fused-silica fiber. ID analysis was performed using a laboratory-synthesized 198Hg-enriched methylmercury (Me 198Hg) spike. Using selective ion monitoring (SIM) mode, the intensities of Me 202HgPr+ at m/z 260 and Me 198HgPr+ at m/z 256 were used to calculate the m/z ratio at 260/256, which was used to quantify MeHg in NRCC CRM DORM-2 fish tissue. A MeHg concentration of 4.336 +/- 0.091 microg g(-1) (one standard deviation, n = 4) as Hg was obtained in DORM-2, in good agreement with the certified value of 4.47 +/- 0.32 microg g(-1) (95% confidence interval). A concentration of 4.58 +/- 0.31 microg g(-1) was determined by standard additions calibration using ethylmercury (EtHg) as an internal standard. The three-fold improvement in the precision of measured MeHg concentrations using ID highlights its superiority in providing more precise results compared to the method of standard additions. A method detection limit (3 S.D.) of 0.037 microg g(-1) was estimated based on a 0.25 g subsample of DORM-2.

Electrospray mass spectrometry of trimethyllead and triethyllead with in-tube solid phase microextraction sample introduction

A study of positive ionization electrospray mass spectrometry (ES-MS) was performed on trimethyllead (TML) and triethyllead (TEL). The system consisted of in-tube solid phase microextraction (SPME) coupled directly to an electrospray mass spectrometer. Fragmentation patterns of compounds were observed by applying different fragmentation voltages. High voltages produced sufficient fragmentation to elucidate the dissociation of the trialkyllead compounds. Electrospray mass spectrometry has been shown to be a suitable detection system for organolead speciation. Applying fragmentation energy programming, it might be possible to obtain in parallel the molecular and atomic signals of lead compounds. Copyright 1999 John Wiley & Sons, Ltd.

UV/spray chamber for generation of volatile photo-induced products having enhanced sample introduction efficiency

A combined spray chamber/UV photolysis unit is described which is shown to substantially enhance sample introduction efficiency for several elements in the presence of 1–5% concentrations of formic, acetic and propionic acids. Enhancement factors of 2–40-fold were achieved for Ag, As, Se, Sb, Hg, I, Bi, Pb and Sn when the aerosol field within the cyclonic chamber produced during conventional concentric nebulizer sample introduction was illuminated by an axially placed 6 W mercury pen lamp. UV photolysis of the organic acids likely initiates radical reactions, generating volatile analyte species.