Speciation of alkylated metals and metalloids in the environment

The analytical methodology for speciation of metals and metalloids associated with alkyl groups and biomacromolecules is critically reviewed. Alkylated metals and metalloids are not only known to be produced by microbial methylation within most anaerobic compartments in the environment, but also in the course of enzymatic transformations during human metabolism. Because of the toxicological relevance of these compounds present in trace to ultratrace concentrations, firm species identification and exact quantification are essential. While many instrumental techniques coupling chromatography (GC, HPLC, CE, GE) with plasma mass spectrometry (ICP-MS) are available for quantification, methods used for structural identification often suffer from inadequate sensitivity (EI-MS, ESI-MS, MALDI-MS, FT-ICRMS). Other problems encountered are sample derivatisation artefacts, lack of suitable standards for quantification, lack of equilibrium between spikes and sample, and the integrity of metal–protein association during separation, in particular during SDS-PAGE. Selected application examples with respect to mercury and arsenic speciation will be discussed critically.      

Intake and excretion of disodium monomethylarsonate in horses: a speciation study

Capillary electrophoresis coupled to inductively coupled plasma mass spectrometry was used in a speciation study on disodium monomethylarsonate (DS-MMA^V) and its metabolites in horses, to which the drug was administered by intramuscular injection on five consecutive days at a single arsenic dosage of 270 mg day⁻¹. Samples of urine, whole blood, plasma, and mane hair were analyzed before, during, and after drug administration. The data show that blood clearing and urinary excretion of MMA is a fast process following first-order kinetics with biological half-lives of about 38 h and 44 h for urine and plasma, respectively. In the time period of 9 days studied, the only metabolite detected in urine was dimethylarsinic acid (DMA^V), which 4 days after the last drug administration accounted for up to 75% of the total excreted arsenic species. This shows, for the first time, that biomethylation of MMA^V to DMA^V is the principal metabolic pathway of this drug in horses. Although DS-MMA^V was administered only during a short 5-day period, an up to six fold increase of arsenic could be measured in the newly grown mane hair.     

Biomethylation of tin (II) complexes in the presence of pure strains of Saccharomyces cerevisiae

The methylation of several tin compounds by strains of Saccharomyces cerevisiae strains (yeast) is described. The production of the methyl tin species was established by gas chromatography and mass spectrometry. Monomethyl tin (IV) products dominated but some dimethyl tin products were observed. This appears to be the first report of a tin methylation by a pure strain of a methylating species rather than a complex mixture obtained from an environmental source.     

金属的生物甲基化作用和环境输送

讨论了生命体与重金属间的相互关系、重金属生物甲基化作用的环境输送及生物富集，评述了重金属的生态危害么及微生物在其环境输送过程中所起的作用。