Investigation into mercury bound to biothiols: structural identification using ESI–ion-trap MS and introduction of a method for their HPLC separation with simultaneous detection by ICP-MS and ESI-MS

Mercury in plants or animal tissue is supposed to occur in the form of complexes formed with biologically relevant thiols (biothiols), rather than as free cation. We describe a technique for the separation and molecular identification of mercury and methylmercury complexes derived from their reactions with cysteine (Cys) and glutathione (GS): Hg(Cys)2, Hg(GS)2, MeHgCys, MeHgGS. Complexes were characterised by electrospray mass spectrometry (MS) equipped with an ion trap and the fragmentation pattern of MeHgCys was explained by using MP2 and B3LYP calculations, showing the importance of mercury–amine interactions in the gas phase. Chromatographic baseline separation was performed within 10 min with formic acid as the mobile phase on a reversed-phase column. Detection was done by online simultaneous coupling of ES-MS and inductively coupled plasma MS. When the mercury complexes were spiked in real samples (plant extracts), no perturbation of the separation and detection conditions was observed, suggesting that this method is capable of detecting mercury biothiol complexes in plants

Improvement of analytical performances for mercury speciation by on-line derivatization, cryofocussing and atomic fluorescence spectrometry

cited By 49International audienceA modified automated on-line hyphenated system for simultaneous inorganic ionic mercury (Hg2+) and monomethylmercury (MeHg+) analysis by hydride generation (HG) or ethylation (Eth), cryofocussing, gas chromatography (GC) separation and atomic fluorescence spectrometry (AFS) detection has been improved. Both derivatization methods are investigated with respect to the chromatographic and analytical performances. They can be both affected by interferences when the AFS detection system is used. Water vapor removal using a soda lime moisture trap improves significantly the chromatographic performances, the reproducibility and the detection limits for Hg2+ and MeHg+ analyzed with both methods. For ethylation (Eth) derivatization, a scattering interference generated from low-quality ethylation reagent has also been eliminated. For HG, improved detection limits are 0.13 ng l-1 and 0.01 ng l-1 for Hg2+ and MeHg+, respectively (0.11 water sample), and reproducibility are 5% for Hg2+ (20 ng l-1) and MeHg+ (5 ng l -1). Improved detection limits for Eth are 0.22 ng g-1 for Hg2+ and 0.02 ng g-1 for MeHg+ (1 g dry sediment sample) and the reproducibility are 5-6% for Hg2+ and MeHg+ (1-2 ng g-1). © 2003 Elsevier B.V. All rights reserved

Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

cited By 21International audienceThe concentration levels of mercury (Hg) species in natural Water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury

Speciation analysis of mercury in aquatic environment

cited By 44International audienceThis review considers methods for mercury speciation with low limits of detection that can be applied to real aquatic environmental samples (waters, sediments, biological tissues). Special attention is given to the necessity of clean sampling procedures and the proper storage of the samples. In this review, different extraction techniques for sediments and biological tissues are considered. The performance of different separation techniques, like liquid chromatography and off-line and on-line gas chromatography, are compared for their environmental applications

Mercury speciation in whole blood by gas chromatography coupled to ICP-MS with a fast microwave-assisted sample preparation procedure

A simple and fast method is described for simultaneous determination of methylmercury (MeHg), ethylmercury (Et-Hg) and inorganic mercury (Ino-Hg) in blood samples by using capillary gas chromatography-inductively coupled plasma mass spectrometry (GC-ICP-MS) after derivatization and alkaline digestion. Closed-vessel microwave assisted digestion conditions with tetramethylammonium hydroxide (TMAH) have been optimized. Derivatization by using ethylation and propylation procedures have also been evaluated and compared. The absolute detection limits (using a 1 mu L injection) obtained by GC-ICP-MS with ethylation were 40 fg for MeHg and Ino-Hg, respectively, and with propylation were 50, 20 and 50 fg for MeHg, Et-Hg and Ino-Hg, respectively. Method accuracy is traceable to Standard Reference Material (SRM) 966 Toxic Metals in Bovine Blood from the National Institute of Standards and Technology (NIST). Additional validation is provided based on the comparison of results obtained for mercury speciation in blood samples with the proposed procedure and with a previously reported LC-ICP-MS method. With the new proposed procedure no tedious clean-up steps are required and a considerable improvement of the time of analysis was achieved compared to other methods using GC separation

Chemical availability of mercury in stream sediments from the Almaden area, Spain

cited By 37International audienceThe chemical speciation, fractionation and availability of mercury in sediments from a cinnabar mining area (Almaden, Spain) was studied with different extraction and analytical procedures, in order to determine the degree to which the ecosystem is harmed by this pollutant. Three total extraction procedures, a sequential extraction and the speciation of organo-mercury compounds were performed in nine sediment samples. In the study area, although concentrations of mercurycan be extremely high (up to 1000 mg kg-1), no organo-mercury compounds were detected (< 2 μg kg-1) and the availability of this element seems restricted. One of the methods for total extraction presented considerably lower recovery in Almaden's sediments, yet the results were controlled with certified reference materials. This disagreement was attributed to the fact that the mercury is in a refractory form. Sequential extraction was able to show that most of the mercury is associated with sulfides (probably as metacinnabar) or in the residual refractory phase (probably as red cinnabar)

Investigation on mercury contamination pathways using model aquatic ecosystems

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