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Detection of volatile organometal chloride species in model atmosphere above seawater and sediment.

The principal route for release of organometallic species into the atmosphere is currently considered to be the biological or chemical formation of saturated volatile compounds such as dimethylmercury, metal hydrides, etc. Model experiments conducted in our laboratory pointto the release of extremely toxic, volatile organotin, -lead, -mercury, and -arsenic species that have been detected as the chlorides in the gas phase above seawater and sediment mixtures. As the sediment was sterilized prior to the analytical study, any bioformation of volatile metal species was excluded. The most probable account of these observations is the naturally occurring formation of metal chlorides, fueled by the abundance of chloride ion (or other halides) present in seawater and many other natural environments. This raises the suggestion that the release of toxic trace elements to the atmosphere by environmental processes may be seriously underestimated. A conservative projection, based on laboratory data, suggests that the emission of butyltin into the atmosphere may reach as high as 150 ng/m2 of water/yr from a polluted marine environment, suggesting a very significant level of release of butyltin from seawater at the global level. For the sampling and determination of volatile metal species, solid-phase microextraction combined with inductively coupled plasma time-of-flight mass spectrometry has been used. This new analytical system is capable of detection of semivolatile, thermally unstable compounds such as the class encompassing metal halide species.