Gas chromatography coupled with atomic absorption spectrometry - A sensitive instrumentation for mercury speciation

New instrumentation for the speciation of mercury is described, and is applied to the analysis of natural water samples. The separation of mercury species is effected using gas chromatography of derivatized mercury species on a widebore capillary column. The solvent is vented using a bypass valve and the separated mercury species are pyrolysed on-line at 800 degrees C for production of mercury atoms. These are then detected by atomic absorption spectrometry (AAS) at the 253.7 and 184.9 nm lines simultaneously in a quartz cuvette. The use of the 184.9 nm line provides a more than five-fold increase in sensitivity compared with the conventional 253.7 nm line and an absolute detection limit of 0.5 pg of mercury. The dynamic range of the combined analytical lines provides a linear response over more than three orders of magnitude. A number of organic compounds not containing mercury are also detected following pyrolysis, especially at the 184.9 nm line. These background species must not co-elute at the retention times for methyl- and inorganic mercury, as otherwise a positive interference would result. By maximizing the chromatographic resolution and minimizing the band broadening in the cuvette by use of a make-up gas, the retention times of interest are freed from co-eluting background peaks. The instrumentation has been applied to the determination of ng 1(-1) concentrations of methyl- and inorganic mercury in Lake Constance, Germany and within the Lake Constance drinking water supply organization, Bodenseewasserversorgung (BWV). The accuracy for the sum of methyl- and inorganic mercury has been assessed by comparison with an independent method for total mercury based on AAS detection implemented at BWV. Relative detection limits using 1 litre water samples and 15 mi injections of the final hexane extract were 0.03 ng 1(-1) for methylmercury and 0.4 ng 1(-1) for inorganic mercury based on the 3j criterion.