Abstract
A number of elements in the fourth, fifth and sixth group of the periodic system form hydrides upon reduction with sodium borohydride, which are stable enough to be of use for chemical analysis (Ge, Sn, Pb, As, Sb, Se, Te). Of these elements, we have investigated in detail arsenic, antimony, germanium and tin. The inorganic and organometallic hydrides are separated by a type of temperature-programmed gas-chromatography. In most cases it is optimal to combine the functions of the cold trap and the chromatographic column in one device. The hydrides are quantified by a variety of detection systems, which take into account the specific analytical chemical properties of the elements under investigation. For arsenic, excellent detection limits (≅40 pg) can be obtained with a quartz tube cuvette burner which is positioned in the beam of an atomic absorption spectrophotometer. For some of the methylarsines, similar sensitivity is available by an electron capture detector. The quartz-burner/AAS system has a detection limit of 90 pg for tin; for this element much lower limits (≅10 pg) are possible with a flame photometric detection system, which uses the extremely intense emission of the SnH molecule at 609.5 nm. The formation of GeO at the temperatures of the quartz tube furnace makes this device quite insensitive for the determination of germanium. Excellent detection limits (≅140 pg) can be reached for this element by the combination of the hydride generation system with a modified graphite furnace/AAS.
The application of these techniques has led to the discovery of a number of organometallic species of arsenic, tin and antimony in the marine environment. Germanium has not been observed to form organometallic compounds in nature. Some aspects of the geochemical cycles of these elements which have been elucidated by the use of these methods will be discussed.
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Andreae, M.O. (1983). The Determination of the Chemical Species of Some of the “Hydride Elements” (Arsenic, Antimony, Tin and Germanium) in Seawater: Methodology and Results. In: Wong, C.S., Boyle, E., Bruland, K.W., Burton, J.D., Goldberg, E.D. (eds) Trace Metals in Sea Water. NATO Conference Series, vol 9. Springer, Boston, MA. https://doi.org/10.1007/978-1-4757-6864-0_1
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