In this study a method for the determination of low methyl mercury (CH3Hg+) concentrations in non-filtered
humic-rich natural water samples using an ethylation-purge and trap with isotope dilution GC-ICP-MS was
developed. Purge and trap systemwas connected on-line to GCwhich was then coupled to ICP-MSwith a simple
non-heated in-house made interface. Samples analyzed in this study contained high amounts of dissolved
organic matter (16–83mg DOC L−1) which is known to interact strongly with mercury affecting the ethylation
efficiency. Thus, prior to instrumental determination CH3Hg+ was separated from the interfering matrix using
a nitrogen-assisted distillation. Isotopically enriched spike was added to samples prior to distillation to correct
the incomplete analyte recovery during the whole analysis procedure. The method detection limit for a 20mL
sample volume was 0.05 ng L−1 (3σ). The method precision obtained by replicate analyses of natural water
samples was found to be better than 10% (RSD). Since there is no certified reference material available for lowlevel
CH3Hg+ in water, the accuracy of the method was verified by comparing the results with the results
obtained with gas chromatography — cold vapor atomic fluorescence spectrometry (GC-CV-AFS) based on the
EPA method 1630. The results obtained with the two different methods were in good agreement with each
other (r2=0.87, n=25) and the method was successfully applied to non-filtered humic-rich natural waters.