The use of species-specific isotopic tracers for inorganic and methyl mercury has allowed the simultaneous determination of the methylation and demethylation potentials of pure culture of isolated sulfate-reducing (SR) bacterial strains using low Hg species concentration levels (7 µg/L (199)Hg(II), 1 µg/L Me(201)Hg). A major advantage of the method reported here is that it can be used to follow simultaneously both the degradation of the species added but also the formation of their degradation products and thus the determination during the same incubation of the specific methylation/demethylation yields and rate constants. Methylation/demethylation capacities and extents have been found to differ between the tested strains and the tested conditions. The methylating/demethylating capacities of bacteria appear to be strain specific. All the methylating strains were found to demethylate methylmercury (MeHg). The active mechanism responsible for Hg methylation appears directly dependent on the bacterial activity but is not dependent on the metabolism used by the tested bacteria (sulfate reduction, fermentation, or nitrate respiration). The results provide confirmation that SR strains contribute to MeHg demethylation under anoxic conditions, leading to Hg(II) as the end product, consistent with the oxidative degradation pathway. Kinetic experiments have allowed specific transformation rate constants to be addressed for the two reversible processes and the reactivity of each isotopic tracer to be compared. The differential reactivity highlighted the different steps involved in the two apparent processes (i.e., uptake plus internal transformation of mercury species). Methylation appears as the slowest process, mainly controlled by the assimilation of Hg(II), whereas demethylation is faster and not dependent on the MeHg concentration.
The capabilities of National Metrology Institutes (NMIs -those which are members of the Comité Consultatif pour la Quantité de Matière (CCQM) of the CIPM) and selected outside "expert" laboratories to quantitate (C 4 H 9 ) 3 Sn + (TBT) in a prepared marine sediment were assessed. This exercise was sanctioned by the 7th CCQM meeting, April 4-6, 2001, as an activity of the Inorganic Analysis Working Group and was jointly piloted by the Institute for National Measurement Standards of the National Research Council of Canada (NRC) and the Laboratory of the Government Chemist (LGC), UK. A total of 11 laboratories submitted results (7 NMIs, and 4 external labs). Two external laboratories utilized a standard calibration approach based on a natural abundance TBT standard, whereas all NMIs relied upon isotope dilution mass spectrometry for quantitation. For this purpose, a species specific 117 Sn-enriched TBT standard was supplied by the LGC. No sample preparation methodology was prescribed by the piloting laboratories and, by consequence, a variety of approaches was adopted by the participants, including mechanical shaking, sonication, accelerated solvent extraction, microwave assisted extraction and heating in combination with Grignard derivatization, ethylation and direct sampling. Detection techniques included ICP-MS (with GC and HPLC sample introduction), GC-MS, GC-AED and GC-FPD. Recovery of TBT from a control standard (NRCC CRM PACS-2 marine sediment) averaged 93.5±2.4% (n=14). Results for the pilot material averaged 0.680±0.015 µmol kg -1 (n=14; 80.7±1.8 µg kg -1 ) with a median value of 0.676 µmol kg -1 . Overall, performance was substantially better than state-of-the-art expectations and the satisfactory agreement amongst participants permitted scheduling of a follow-up Key comparison for TBT (K-28), a Pilot intercomparison for DBT (P-43), and certification of the test sediment for TBT content and its release as a new Certified Reference Material (HIPA-1) with a TBT content of 0.679±0.089 µmol kg -1 (expanded uncertainty, k=2, as Sn) (80.5±10.6 µg kg -1 ).
Isotope-dilution analysis in combination with GC-ICP-MS detection has been applied to the determination of butyltin species in environmental samples. Different spikes containing the isotopically labeled butyltin species have been synthesized in the laboratory after optimization of the reaction conditions. The isotopic compositions of the tin species in the different spike solutions were determined by GC-ICP-MS after derivatization by aqueous ethylation with sodium tetraethylborate. Reverse isotope-dilution analysis was used for quantitation of the spike solutions by means of natural MBT, DBT, and TBT standards. The mixed spikes were used for simultaneous analysis of MBT, DBT and TBT in the certified reference materials, PACS-2, CRM 462, and CRM 646, with satisfactory results. The excellent agreement of the different speciation results obtained by use of the different spikes is a good indicator of the precision, accuracy, and reliability which can be achieved by using isotope-dilution analysis for trace metal speciation. Application of a double spike containing (119)Sn-enriched MBT (79.7 At%), (118)Sn-enriched DBT (86.7 At%), and (119)Sn-enriched TBT (83.1 At%) also enabled evaluation of the conditions resulting in quantitative extraction of the species from the solid matrix, in combination with possible alterations depending on the different extraction procedures used (mechanical shaking, ultrasounds, and microwaves). Mathematical equations used for this purpose computed the correct species concentrations directly and, additionally, the decomposition factors (from TBT to DBT and from DBT to MBT) after precise measurement of the (119)Sn/(120)Sn and (118)Sn/(120)Sn ratios for all butyltin species by GC-ICP-MS.
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