Phosphine and phosphides are reported to occur at numerous environmental sites such as fresh and marine sediments, landfills, faecal matter, biogas digesters and soils. The concentrations are several log units lower than the time-weighted average exposure standard, i.e. in the order of ng per m(3) of gas or ng per kg material. Research about the biological formation of highly reduced gaseous phosphorus compounds dates back more than a hundred years. The early reports had to deal with a lot of scepticism. Thanks to new analytical tools (gas chromatography) it has become clear, during the last decade, that phosphine is a global constituent of the atmosphere. Pure strains of micro-organisms cultivated under highly anaerobic conditions were shown to produce phosphine. Thermodynamic considerations indicate that it is very improbable that the reduction of phosphate to phosphine is endergonic. Therefore the generation of phosphine cannot be compared with sulphidogenesis and methanogenesis. There seems to be a link between the existence of highly reactive gaseous phosphorus compounds and increased levels of metal corrosion. The reactive compounds could be formed by micro-organisms or they are liberated from phosphorus-containing impurities in the iron by the action of bacterial metabolites. The biochemical pathways responsible for the production of gaseous phosphorus compounds have not been characterised yet.