The speciation of mercury and organomercury compounds by high performance liquid chromatography/atmospheric pressure ionization mass spectrometry

Harrington, Christopher F.; Romeril, Julie; Catterick, Tim

doi:10.1002/(sici)1097-0231(19980731)12:14<911::aid-rcm254>3.0.co;2-x

Cited by 24 publications

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References 5 publications

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“…A few papers study the behavior of mercury-and alkylmercury-thiol amino acid systems by mass spectrometry [13][14][15][16][17]; in particular D'Agostino and coworkers [13,14] questioned, at least in part, the formation of sulfur-bound mercury species as the sole form of mercury-amino acid and peptide interaction. The formation of mercuriated species has been observed in the deprotection of solid phase synthetized cysteine-containing peptides and the corresponding products have been characterized by ESI and tandem mass spectrometry [15,16].…”

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confidence: 99%

“…The formation of mercuriated species has been observed in the deprotection of solid phase synthetized cysteine-containing peptides and the corresponding products have been characterized by ESI and tandem mass spectrometry [15,16]. A recent analytical method for the LC-MS determination of mercury(II) and alkyl-mercury species has been described [17], whereby ␤-mercapto-ethanol is added to the mobile phase to yield stable alkyl-Hg-S-CH 2 -CH 2 -OH species, which can be efficiently protonated by atmospheric pressure chemical ionization.…”

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confidence: 99%

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Molecular characterization of homo- and heterodimeric mercury(II)-bis-thiolates of some biologically relevant thiols by electrospray ionization and triple quadrupole tandem mass spectrometry

Rubino

Verduci

Giampiccolo

et al. 2004

J. Am. Soc. Mass Spectrom.

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A series of 24 compounds of general formula R(1)S-Hg-SR(2), R(1) and R(2) being biologically relevant thiol-containing amino acids and peptides (cysteine, homo-cysteine, penicillamine, N-acetyl-cysteine, N-acetyl-penicillamine, cysteinyl-glycine, gamma-glutamyl-cysteine and glutathione) were prepared by direct reaction of mercury(II) ions and thiols in water at millimolar concentration. The obtained products were characterized by electrospray ionization and triple quadrupole tandem mass spectrometry. The source spectra of equimolar mixtures of two different thiols reacting with a stoichiometric amount of mercury(II) show the peak clusters of the three theoretically expected bis-thiolato-mercury(II) complexes with relative intensities close to the theoretically expected 1:2:1 ratio, thus pointing at lack of substantial discrimination between the different thiols, the only observed exception being homo-cysteine, which is less reactive than cysteine and penicillamine. The fragment spectra are structure-specific for the different ligands bound to the metal ion and allow a stand-alone discrimination of some constitutional isomer pairs. Among the peculiar fragmentation processes observed, loss of neutral ammonia from protonated symmetrical and unsymmetrical mercury(II)-bis-thiolates with free, protonizable amino groups leads to the formation of thiirane-carboxylic bound species; this process is suppressed when the protonated amino group is in the gamma-position with respect to the sulfur atom, as in the case of compounds with homo-cysteine. This unusual behavior may hint at unforeseen mechanisms for the interaction of mercury(II) with biological structures, ultimately leading to cellular and organ toxicity. Compounds with N-acetylated amino acids show distinctive fragment ions to which the connectivity of a protonated 2-methyl-oxazoline-5-carboxylic acid may be proposed on the basis of the loss of water and of the elements of formic acid. Finally, the adducts of mercury(II) with glutathione and gamma-glutamyl-cysteine feature a distinctive decomposition channel by loss of a pyroglutamic unit, much the same as protonated glutathione, glutathione disulfide, the S-glutathionyl adducts of biologically occurring electrophiles and other (pseudo)-peptides with gamma-glutamyl bonds.

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Molecular characterization of homo- and heterodimeric mercury(II)-bis-thiolates of some biologically relevant thiols by electrospray ionization and triple quadrupole tandem mass spectrometry

Rubino

Verduci

Giampiccolo

et al. 2004

J. Am. Soc. Mass Spectrom.

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“…The response variable evaluated was the methylmercury fluorescence signal obtained for a 2 g dm −3 aqueous solution. This concentration was considered acceptable in comparison to other HPLC optimisation works: 40 g dm −3 [16]; 250 g dm −3 [15], and 10 × 10 3 g dm −3 [20]. The experiments were performed in three replicates.…”

Section: Sequential Simplex Methodsmentioning

confidence: 99%

“…Coupled with GC, a large variety of mercury detection and quantification methods have been used: electron capture detection (ECD) [1]; microwave induced plasma (MIP) [2][3][4]; atomic fluorescence spectrometry (AFS) [5][6][7]; atomic absorption spectrometry (AAS) [8,9]; inductively coupled plasma-mass spectrometry (ICP-MS) [10,11]; and glow discharge atomic emission spectrometry (GD-AES) [12]. Coupled with HPLC, the detection and quantification methods for mercury speciation have included: ICP-MS [13]; photometry [14]; cold vapour atomic absorption spectrometry (CV-AAS) [15]; cold vapour atomic fluorescence spectrometry (CV-AFS) [16,17]; atomic emission spectrometry (AES) [18,19]; and atmospheric pressure ionisation mass spectrometry (API-MS) [20]. Although GC has been the most widely used separation technique in mercury speciation studies, it is necessary to perform column passivation by repeated mercury salt injections [21] and derivatisation of mercury compounds to form volatile species [22].…”

Section: Introductionmentioning

confidence: 99%

Simple methodology for methylmercury and inorganic mercury determinations by high-performance liquid chromatography–cold vapour atomic fluorescence spectrometry

Ramalhosa

Segade

Pereira

et al. 2001

Analytica Chimica Acta

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“…The chromatographic conditions used during the study are detailed in Table 1 and were adapted from those of Harrington et al 11 previously developed for the analysis of methylmercury in fish tissue by liquid chromatography coupled to atmospheric pressure chemical ionization mass spectrometry (HPLC-APCI-MS). Each of the three sample replicates for the IMEP sample, the tuna fish CRM and the hair CRM were analysed interspersed with injections of the mobile phase and the reagent blank solution, to eliminate the possibility of analyte carry over between samples.…”

Section: Instrumental Analysismentioning

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The determination of methylmercury in biological samples by HPLC coupled to ICP‐MS detection

Vidler

Jenkins

Hall

et al. 2006

Applied Organom Chemis

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The use of high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) for the determination of methylmercury (MeHg + ) in fish tissue and hair samples is described. Analysis of these sample types is required when carrying out biomonitoring studies to determine human dietary exposure to this toxic mercurial compound. The developed method used a mobile phase containing an organic modifier and a sulfydryl compound (1 : 1 v/v methanol : water containing 0.01% v/v 2-mercaptoethanol) to limit peak tailing and aid separation. The chromatographic separation was coupled to the ICP-MS detector via a short piece of PEEK tubing, attached to the nebulizer. A cooled spraychamber and oxygen addition post-nebulization were required to limit the solvent loading on the plasma and reduce carbon build-up on the cones, respectively. The sample preparation procedure employed a drying step followed by digestion of the sample using tetramethylammonium hydroxide (TMAH) and heating in an open vessel microwave system. Two fish tissue certified reference materials (CRM), tuna fish CRM 463 and 464 (BCR, Brussels), a tuna fish proficiency test sample, IMEP-20 (IRMM, Geel, Belgium) and a hair CRM NIES no. 13 (National Institute of Environmental Science, Japan), were used to evaluate the method. The recovery of MeHg + for these four materials was between 83 and 100%, with precisions better than 6% for three separate extractions of the different materials. The limit of quantitation for MeHg + using the developed protocol was 0.5 µg Hg g −1 . The stability of MeHg + in the fish sample extracts was also assessed and losses of 14-16% were observed after storage of the extracts in a refrigerator at 5 • C, in high-density polypropylene tubes, for 6 months. The developed protocol has been used previously with atmospheric pressure ionization mass spectrometry (API-MS) to provide structural characterization and also with calibration via isotope dilution (IDMS) to provide high accuracy quantitation. Copyright forms of an element becomes apparent when considering its toxicity and environmental bioavailability. This is particularly true for the heavy metal mercury because of the acute toxicity of all the chemical species, which has resulted in a number of fatal poisoning instances throughout the world.2,3 Methylmercury (MeHg + ) is notable in this respect, because it is readily formed from inorganic mercury (Hg 2+ ) by natural environmental processes, can be absorbed across the gastrointestinal tract, cross the blood-brain barrier and can pass between mother and fetus. These characteristics can lead to an accumulation of MeHg + in fetal blood, resulting in neurological impairment of the newborn. Speciation Analysis and EnvironmentThe main source of non-acutely toxic MeHg + in the general population is the dietary intake of certain species of fish and other marine life, 5 most notably those at the top of the ecological food chain. The monitoring of mercury in the tissue of edible fish is important becau...

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The speciation of mercury and organomercury compounds by high performance liquid chromatography/atmospheric pressure ionization mass spectrometry

Cited by 24 publications

References 5 publications

Molecular characterization of homo- and heterodimeric mercury(II)-bis-thiolates of some biologically relevant thiols by electrospray ionization and triple quadrupole tandem mass spectrometry

Molecular characterization of homo- and heterodimeric mercury(II)-bis-thiolates of some biologically relevant thiols by electrospray ionization and triple quadrupole tandem mass spectrometry

Simple methodology for methylmercury and inorganic mercury determinations by high-performance liquid chromatography–cold vapour atomic fluorescence spectrometry

The determination of methylmercury in biological samples by HPLC coupled to ICP‐MS detection

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