A simple technique is described for the rapid determination of methylmercury in fish tissue. Following simple dissolution in methanolic KOH solution, aqueous phase ethylation by derivatization with NaB(C2H5)4, cryogenic trapping on a packed chromatographic column, and GC separation, volatile mercury species are detected by atomic absorption spectrometry. Absolute detection limits are 4 pg of Hg for CH3Hg+ and 75 pg of Hg for labile Hg2+. Concentration detection limits for this optimized procedure are 4 ng of Hg for CH3Hg+ and 75 ng of Hg for labile Hg2+ per gram of pulverized dried fish tissue. Analysis of standard reference materials demonstrates the accuracy, precision, and reproducibility of the analytical method.
Levels and patterns of C1-C4/C9 organic nitrates were measured for the first time in Antarctica. The sampling was done by adsorptive enrichment on Tenax TA followed by thermodesorption cold-trap high resolution capillary gas chromatography with electron capture detection. 2-70 l air on-column have been analyzed this way. C1-C9 alkyl mononitrates, C2-C4 alkyl dinitrates, C2-C4 hydroxy alkyl nitrates, and halocarbons could be identified in air samples collected near the German Neumayer Research Station, Antarctica, in February 1999. Volatile biogenic and anthropogenic halocarbons were used to assess the origin of the air parcels analyzed. The average concentration measured for P C2-C6 alkyl nitrates was in the range of 9:2 AE 1:8 ppt(v), while the sum of the mixing ratios of six C2-C4 hydroxy alkyl nitrates was in the range of 1:1 AE 0:2 ppt(v). Moreover, C2-C4 alkyl dinitrates were found at levels near the detection limit of 0.1-0.5 ppt(v). The concentrations of organic nitrates found in Antarctic air represent ultimate baseline levels due to chemical and physical loss processes during long-range transport in the air. The South Atlantic and the Antarctic Ocean as a general secondary source for organic nitrates in terms of an air/sea exchange equilibrium has to be evaluated yet, but it seems logical. Our results confirm the common assumption that there are no biogenic marine sources of C2-C9 organonitrates. We have found a level of >80 ppt(v) for methyl nitrate. This level if it can be confirmed in a systematic survey requires a strong biogenic source of methyl nitrate in the Antarctic Ocean.
We have detected volatile species of silicon, vanadium, arsenic, bromine, tin, antimony, tellurium, iodine, mercury, lead and bismuth in gases released from domestic waste deposits, using inductively coupled argon plasma mass spectrometry (ICPMS). By concurrent aspiration of a multielement standard solution for calibration, the element concentrations in deposit gas are found to be in the range from 0.1 ng m-3 to 10 pg m-3 gas. The global amount of some metal species emitted by this process may be of the order of several tons per year. These results suggest a biogeochemical pathway for the transfer of metals into the atmosphere via volatile species. This process may have significant influence on atmospheric cycling of metals as well as on metal toxicity within ecosystems.
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