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Species specific isotope dilution with on line derivatisation for determination of gaseous mercury species
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2005 (English)In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 20, no 11, 1232-1239 p.Article in journal (Refereed) Published
Abstract [en]

A species specific isotope dilution (SSID) method for determination of the volatile mercury (Hg) species Hg0, (CH3)2Hg, CH3HgX and HgX2(where X is a counter ion) in gaseous samples was developed. The procedure involved on line derivatisation of ionic Hg species with sodium tetraethylborate during sampling, before collection of species on a Tenax TA tube in series with an Au–Pt tube. Collected species were thermally desorbed and determined by GC-ICP-MS. The procedure provided absolute detection limits of 0.5 pg for CH3HgX and (CH3)2Hg, 5 pg for HgX2 and 25 pg for Hg0. Recoveries and transformations of the investigated species were studied for the different procedural steps and the method was tested for microcosm experiments on brackish water sediment samples, as well as for laboratory air samples. As a result of methylation and reduction processes within the sediment, gaseous emission rates could be determined for all investigated species after addition of an isotope enriched aqueous inorganic 199Hg2+ standard to the sediment. Hg0 was the only specie detected in laboratory air samples (4.5 ng m–3). The procedure for derivatisation of ionic Hg species prior to collection on Tenax TA reduces memory effects and transformations of CH3HgX and HgX2, which is especially advantageous at low sample gas flow rates and for complex gaseous matrices, such as emissions from sediment samples. SSID provides simplified methodological development, as well as efficient correction for matrix induced losses and transformations of Hg species. The method could be useful for various biogeochemical studies of Hg, as well as for reliable risk assessments during, for example, waste management and soil remediation.

Place, publisher, year, edition, pages
RCS Publishing , 2005. Vol. 20, no 11, 1232-1239 p.
URN: urn:nbn:se:umu:diva-12910DOI: doi:10.1039/b504678eOAI: diva2:152581
Available from: 2007-04-24 Created: 2007-04-24 Last updated: 2010-11-19Bibliographically approved
In thesis
1. Instrumental and methodological developments for isotope dilution analysis of gaseous mercury species
Open this publication in new window or tab >>Instrumental and methodological developments for isotope dilution analysis of gaseous mercury species
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with instrumental and methodological developments for speciation analysis of gaseous mercury (Hg(g)), based on isotope dilution analysis (IDA). The studied species include Hg0, (CH3)2Hg, CH3HgX and HgX2 (where X symbolises a negatively charged counter ion in the form of a halide or hydroxyl ion). Gas chromatography hyphenated with inductively coupled plasma mass spectrometry (GC-ICPMS) was used for separation and detection of Hg(g) species. Permeation tubes were used for the generation of gaseous isotopically enriched Hg standards (tracers). These tracers were continuously added to the sample gas stream during sampling of Hg(g). A mobile prototype apparatus incorporating both the permeation source and a sampling unit for collection of Hg(g) was developed and used for this purpose. Hg(g) species were pre-concentrated on Tenax TA and / or Carbotrap solid adsorbents. Au-Pt was used for pre-concentration of total Hg(g), either as the primary medium, or as backup. Collected species were eluted from these media and introduced to the instrument by thermal desorption.

Various degrees of species transformations, as well as losses of analyte during pre-concentration and elution, were found to occur for both Tenax TA and Carbotrap. The performance characteristics of these media were shown to be species specific, as well as matrix dependent. The development of an on-line derivatisation procedure allowed for minimised species transformations, as well as reduced adsorption and memory effects of ionic Hg(g) species within the analytical system. In conclusion, IDA provides an important tool for identification, minimisation and correction of the above mentioned analytical problems. Furthermore, it offers significant advantages with respect to quality assurance, compared to conventional techniques, both when it comes to rational development of new methodology, as well as for continuous validation of existing procedures.

The developed methodology for speciation analysis of Hg(g) has been tested in various applications, including the determination of Hg(g) species concentrations in ambient air (both in and outdoor) and in the head space of sediment microcosms. Hg(g) species were formed in the sediments as a result of naturally occurring redox and methylation processes, after addition of an isotope enriched aqueous Hg(II) precursor. The methodology has also been used for assessing the risk of occupational exposure to Hg(g) species during remediation of a Hg contaminated soil and for studying Hg0(g) transport and Au-Pt pre-concentration characteristics in natural gases. Hg0 was used as the model species in the latter experiments, since it is believed to be the dominating form of Hg(g) in natural gas. The results indicate that the occurrence of H2S can cause temperature dependent adsorption and memory effects of Hg0(g) in the presence of stainless steel, thereby providing a plausible explanation to the variability of results for sour gases occasionally observed in the field. Hg0(g) has demonstrated overall high recovery during collection on Au-Pt tubes for all gases tested in this thesis. Recent (unpublished) results however indicate that there are potential species specific and matrix dependent effects associated with the Au-Pt based pre-concentration of Hg(g) in natural gases.

Place, publisher, year, edition, pages
Umeå: Kemi, 2007. 46 p.
Mercury, gas, species, speciation analysis, isotope dilution analysis, permeation tubes
National Category
Analytical Chemistry
urn:nbn:se:umu:diva-1448 (URN)978-91-7264-463-2 (ISBN)
Public defence
2007-12-15, Lilla hörsalen, KBC, 90187, Umeå, 13:00 (English)
Available from: 2007-11-22 Created: 2007-11-22 Last updated: 2010-11-19Bibliographically approved

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