Instrumentation and methodology for determination of the gaseous mercury species Hg0, (CH3)2Hg, and CH3Hg+ has been developed. The method is based on continuous addition of gaseous isotopically enriched Hg species (tracers) at the point of sample acquisition, in combination with reduced pressure sampling on Carbotrap adsorbent tubes. Permeation tubes are used for generation of the tracers. Collected species are thermally desorbed and purged through an aqueous sodium tetraethylborate solution for derivatization of CH3Hg+. The purged gas is dried with a Nafion membrane, and the Hg species are subsequently collected on a smaller Tenax TA adsorbent tube. Species are then thermally desorbed from the Tenax TA and introduced into a gas chromatograph connected to an inductively coupled plasma mass spectrometer for separation and detection. To be able to add tracers during field sampling, we developed a portable device, supplying the permeation tubes with a thermostated and mass flow-controlled air stream of 5.0 ± 0.1 C and 50.0 mL min-1, respectively. Typical permeation rates obtained during a period of more than 6 weeks were 12.93 ± 0.56, 0.42 ± 0.01, and 0.49 ± 0.03 (mean ± standard deviation) pg of Hg min-1 for a set of 199Hg0, (CH3)2198Hg, and CH3200Hg+ tubes, respectively. Methodological detection limits (3) were determined to 700 pg of Hg m-3 for Hg0 and 50 pg of Hg m-3 for (CH3)2Hg and CH3Hg+. The collection efficiencies for sampled volumes of 400 L of synthetic air on the Carbotrap tubes used in this study were 13 ± 2, 102 ± 2, and 99 ± 4% for Hg0, (CH3)2Hg, and CH3Hg+, respectively. Desorption efficiencies for the above species and tubes were 98 ± 2, 98 ± 1, and 90 ± 4%, respectively. Fractions (20-40%) of the added (CH3)2198Hg and CH3200Hg+ tracers were found to be transformed during the analytical processing of collected air samples. Determined concentrations in the research laboratory air, corrected for species transformations, were 3-53, 8-11, and 1-2 ng of Hg m-3 for Hg0, (CH3)2Hg, and CH3Hg+, respectively. Concentrations in the ambient air were determined to be 2.1-2.6 ng m-3 for Hg0 and below the detection limit for (CH3)2Hg and CH3Hg+.
ACS publications , 2003. Vol. 75, no 20, 5584-5591 p.