Arsenic speciation by capillary gas-liquid chromatography

Specific environmentally significant arsenic compounds are determined by capillary gas-liquid chromatography. Inorganic (arsenite, arsenate) and organic (monomethylarsonate, dimethylarsinate) arsenicals are measured as the corresponding methylthioglycolate derivatives, which are simultaneously separated on wide-bore borosilicate glass and fused-silica columns under conditions of temperature programming. Inorganic arsenate and arsenite cannot be differentiated by the derivatization technique. Flame-ionization and electron-capture detection are evaluated. A simple and rapid sample preparation procedure is used for water, urine, blood, and tissue.     

Determination and speciation of mercury in a dental work-place by cold vapour atomic absorption spectrometry and gas-liquid chromatography

Cold Vapour Atomic Absorption Spectrometry (CVAAS) and Gas-Liquid Chromatography (GLC) have been used for determination and speciation of mercury. Total mercury, methylmercury, ethylmercury and phenylmercury concentrations in urine samples taken from students and staff of a dental work-place were investigated. Air samples were also analyzed. Detection limits, as three times the standard deviation, and in units of ng analyte per ml urine were found to be 1.7, 12, 2.4 and 21 for total mercury, methylmercury chloride, ethylmercury chloride and phenylmercury chloride, respectively.     

Comparison of gas chromatographic hyphenated techniques for mercury speciation analysis

In this study, we evaluate advantages and disadvantages of three hyphenated techniques for mercury speciation analysis in different sample matrices using gas chromatography (GC) with mass spectrometry (GC-MS), inductively coupled plasma mass spectrometry (GC-ICP-MS) and pyrolysis atomic fluorescence (GC-pyro-AFS) detection. Aqueous ethylation with NaBEt(4) was required in all cases. All systems were validated with respect to precision, with repeatability and reproducibility <5% RSD, confirmed by the Snedecor F-test. All methods proved to be robust according to a Plackett-Burnham design for 7 factors and 15 experiments, and calculations were carried out using the procedures described by Youden and Steiner. In order to evaluate accuracy, certified reference materials (DORM-2 and DOLT-3) were analyzed after closed-vessel microwave extraction with tetramethylammonium hydroxide (TMAH). No statistically significant differences were found to the certified values (p=0.05). The suitability for water samples analysis with different organic matter and chloride contents was evaluated by recovery experiments in synthetic spiked waters. Absolute detection and quantification limits were in the range of 2-6 pg for GC-pyro-AFS, 1-4 pg for GC-MS, with 0.05-0.21 pg for GC-ICP-MS showing the best limits of detection for the three systems employed. However, all systems are sufficiently sensitive for mercury speciation in environmental samples, with GC-MS and GC-ICP-MS offering isotope analysis capabilities for the use of species-specific isotope dilution analysis, and GC-pyro-AFS being the most cost effective alternative.     

Application of gas-liquid chromatography for standardization of herbal raw materials and herbal drugs

Gas chromatography with mass selective detection is described as method for investigation and standardization of herbal raw materials and herbal drugs. Marker compounds and chromatographic conditions are described for some herbs.     

Quantitative measurements of inorganic mercury and organomercurials in water and biological media by gas-liquid chromatography

Gas-liquid chromatography is used to determine inorganic mercury in the presence and absence of organomercurials in water and biological media after alkylation or arylation. Best results for inorganic mercury were realized with pentacyanomethylcobaltate(III) and tetraphenylborate(III), via the generated methyl and phenyl mercurial. Tetraethyltin, forming ethylmercury, was less satisfactory. Lower detection limits with these reagents were in the range 10–30 ng Hg ml^-1 of medium. Co-determination of inorganic mercury and various organomercurials was carried out by sequential or simultaneous procedures with several column temperatures and packings. Optimal Chromatographic results were achieved with Durapak Carbowax 400 (low K') on Porasil F and 10% DEGS on Anakrom SD.     

Organic mercury speciation in fish by capillary gas chromatography interfaced with atomic absorption spectrometry

Summary A rapid method for the speciation of mercury in fish has been described. Organomercurials in benzene extract were separated by glass capillary gas chromatography and detected by atomic absorption spectrometry. Spiked alkylmercury in fish yielded 95% recovery with one single extraction with benzene. The absolute detection limit was about 1.0×10^–10 g mercury. The method can be applied to the determination of 0.04 ppm of mercury in a 0.5 g sample.

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Speziation von organischem Quecksilber in Fisch mit Hilfe der Capillar-Gas-Chromatographie in Verbindung mit AAS

     

Applicability of multisyringe chromatography coupled to cold-vapor atomic fluorescence spectrometry for mercury speciation analysis

In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg(2+)), methylmercury (MeHg(+)) and ethylmercury (EtHg(+)) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3σ) were found to be 0.03, 0.11 and 0.09 μg L(-1) for MeHg(+), Hg(2+) and EtHg(+), respectively. The relative standard deviation (RSD, n=6) of the peak height for 3, 6 and 3 μg L(-1) of MeHg(+), Hg(2+) and EtHg(+) (as Hg) ranged from 2.4 to 4.0%. Compared with the conventional HPLC-CV/AFS hyphenated systems, the proposed MSC-CV/AFS system permitted a higher sampling frequency and low instrumental and operational costs. The developed method was validated by the determination of a certified reference material DORM-2 (dogfish muscle), and was further applied for the determination of mercury species environmental and biological samples.     

A multinjection strategy for mercury speciation

A multiinjection strategy has been developed to increase the sampling throughput of the high-performance liquid chromatography determination of inorganic-mercury, methylmercury, ethylmercury and phenylmercury. The method involves the injection of samples each 3.5 min, in spite of the fact that phenylmercury retention time corresponds to 9.04 min. In the selected conditions, the sampling frequency was 11 h⁻¹ in front of that of 6 h⁻¹, obtained by conventional injection of each sample after the complete elution of Hg species. Additionally, the analytical reagents consumption was reduced drastically in almost 50%. The main characteristics of the chromatographic separation were maintained and only the resolution of phenylmercury was reduced from 10.3 to 1.7 and that of ethylmercury from 4.6 to 3.1.     

Vanadium speciation by ion chromatography

An ion-chromatographic method, using a carbonate-buffered (1,2-cyclohexylenedinitrilo)tetraacetic acid (CDTA) eluant, is described for the simultaneous determination of vanadium(IV) and vanadium(V). Vanadium(IV) was, after pre-column complexation with CDTA, separated from vanadium(V) (as vanadate) by anion-exchange chromatography. The analytical range is 0.5 to 20 g/ml and 0.25 to 10 g/ml for vanadium(IV) and vanadium(V), respectively. Detection limits are estimated to be 145 and 70 ng/ml for vanadium(IV) and vanadium(V), respectively.     

Lattice-fluid model for gas-liquid chromatography

Lattice-fluid models describe molecular ensembles in terms of the number of lattice sites occupied by molecular species (r-mers) and the interactions between neighboring molecules. The lattice-fluid model proposed by Sanchez and Lacombe (Macromolecules, 1978;11:1145-1156) was used to model specific retention volume data for a series of n-alkane solutes with n-alkane, polystyrene, and poly(dimethylsiloxane) stationary liquid phases. Theoretical equations were derived for the specific retention volume and also for the temperature dependence and limiting (high temperature) values for the specific retention volume. The model was used to predict retention volumes within 10% for the n-alkanes phases; 22% for polystyrene; and from 20 to 70% for PDMS using no adjustable parameters. The temperature derivative (enthalpy) could be calculated within 5% for all of the solutes in nine stationary liquid phases. The limiting value for the specific retention volume at high temperature (entropy controlled state) could be calculated within 10% for all of the systems. The limiting data also provided a new chromatographic method to measure the size parameter, r, for any chromatographic solute using characteristic and size parameters for the stationary phase only. The calculated size parameters of the solutes were consistent, i.e. independent of the stationary phase and agreed within experimental error with the size parameters previously reported from saturated vapor pressure, latent heat of vaporization or density data.     

Evaluation of a rapid method for preparation of fatty acid methyl esters for analysis by gas-liquid chromatography

The major limitation to fatty acid analysis by gas-liquid chromatography is associated with preparation of fatty acid methyl esters (FAME). In the present study, FAME preparations were made from plant oils (corn, olive, sunflower), sunflower oil margarine, lard and various animal tissue fats by a rapid transesterification involving tetramethylammonium hydroxide in methanol, and also by a longer conventional saponification-esterification method. Fats from animal (beef, mutton, pork) adipose tissues were extracted by a simpler modified procedure and also by the Folch method prior to the rapid and the conventional FAME preparations, respectively. FAME analysis on a gas-liquid chromatograph equipped with a Silar 10C glass capillary column indicated similar fatty acid composition of a given fat or oil, whether FAME was prepared by the rapid or the longer conventional method. The data obtained by both methods were very highly correlated for all the fats (r = 0.9895 - 0.9999). However, the rapid method showed a tendency for enhanced recoveries of lower chain fatty acids (e.g. 14:0), and also of unsaturated C18 isomers. Possibly, losses of fatty acids that occurred during the lengthy fat extraction, fatty acid esterification or ether-evaporation FAME concentration steps (conventional method) were minimised by the single transesterification step (rapid method). This rapid transesterification method appears to be an attractive alternative to FAME preparation from a wide variety of different fats for gas-liquid chromatographic analysis.     

Multicapillary gas chromatography coupled to inductively coupled plasma-time-of-flight mass spectrometry for rapid mercury speciation analysis

A simple, rapid and accurate method on the basis of multicapillary gas chromatography (MCGC) combined with inductively coupled plasma-time-of-flight mass spectrometry (ICP-TOFMS) was developed for speciation analysis of methylmercury (MeHg⁺) and inorganic mercury (Hg²⁺). The potential of the ICP-TOFMS for transient multi-isotope detection of very short signals (peak width of 0.4 s at half peak height) was evaluated. Two injection systems (purge-and-trap (PTI) and split (SI) injections) were compared in terms of species separation resolution and transient signal profile. Using purge-and-trap injection, after in situ derivatization of the ionic mercury species with sodium tetraethylborate, a baseline separation of MeHg⁺ and Hg²⁺ was achieved within a chromatographic run of <35 s. To correct for matrix-induced ion signal variation and instrumental drift, propylmercury (PrHg⁺) was used as internal standard. Detection limits of 16 and 257 fg g⁻¹ for MeHg⁺ (as Hg) and Hg²⁺, respectively, were achieved. The analytical precision (R.S.D. (%)) for 10 successive injections of a standard mixture containing 10 pg MeHg⁺ (as Hg) and Hg²⁺ was 1.2% for MeHg⁺ and 4.1% for Hg²⁺. The method was validated by analysis of two biological certified reference materials (CRM): a dogfish muscle (DORM-2) and a freeze-dried tuna fish (CRM 464).     

Separation of monosubstituted phenols by gas-liquid chromatography

The factors influencing the separation of monosubstituted phenols on silicone oil, poly(ethylene glycol) (1500), Apiezon L + Bentone 34, squalane, Versamide and diethylhexyl sebacate are discussed. Specific retention volumes, height equivalent to a theoretical plate and thermodynamic quantities are reported. Diethylhexyl sebacate and Versamide are selective for quantitative separation of all the isomers studied.     

Separation of mercaptans by gas-liquid partition chromatography

Summary The quantitative separation of a number of aliphatic mercaptans on an ultra micro scale has been achieved by using theJames- Martin gas-liquid chromatographic technique.

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Zusammenfassung Die quantitative Trennung einer Anzahl aliphatischer Merkaptane ira TJItramikro-maßstab gelang nach dem vonJames undMartin angegebenen Verfahren der Gas-Flüssigkeits-Verteilungschromatographie.

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Résumé La technique chromatographique liquide-gaz deJames-Martin a été employée avec succès pour la séparation quantitative d'un certain nombre de mercaptans aliphatiques à l'échelle ultramicro-analytique.