Gases released from anaerobic wastewater treatment facilities contain considerable amounts of volatile methyl and hydride derivatives of metals and metalloids, such as arsine (AsH 3 ), monomethylarsine, dimethylarsine, trimethylarsine, trimethylbismuth (TMBi), elemental mercury (Hg 0 ), trimethylstibine, dimethyltellurium, and tetramethyltin. Most of these compounds could be shown to be produced by pure cultures of microorganisms which are representatives of the anaerobic sewage sludge microflora, i.e., methanogenic archaea (Methanobacterium formicicum, Methanosarcina barkeri, Methanobacterium thermoautotrophicum), sulfate-reducing bacteria (Desulfovibrio vulgaris, D. gigas), and a peptolytic bacterium (Clostridium collagenovorans). Additionally, dimethylselenium and dimethyldiselenium could be detected in the headspace of most of the pure cultures. This is the first report of the production of TMBi, stibine, monomethylstibine, and dimethylstibine by a pure culture of M. formicicum.Volatile methyl and hydride derivatives of metal(loid)s are found in gases released from natural environments such as sediments, wetlands (40), and hydrothermal springs (26), as well as from anthropogenic environments such as wastewater treatment plants and waste deposits (18). Some of the compounds are of anthropogenic origin, for example, alkylated tin and lead derivatives, whereas others are produced in environmental settings either due to chemical transalkylation or due to biologically mediated methylation and hydride formation (the addition of a formal hydride ion mediated by an organism) (11,36). The production of volatile metal(loid) compounds is a significant part of the biogeochemical cycles of metals (e.g., Bi, Hg, and Sn) and metalloids (e.g., As, Sb, Se, and Te) because of the increased mobility of the resultant compounds. Additionally, most of the volatile derivatives exhibit higher toxicity than their inorganic counterparts, since organic derivatives are lipophilic and are thus more biologically active (35,36). Exceptions are arsenic and selenium, in which cases the inorganic, nonmethylated forms are more toxic than the methylated derivatives (14).Following the pioneering work of Gosio (23) and Challenger et al. (6, 7), the mechanism for the biomethylation of arsenic has been studied extensively with various fungi (10, 15), bacteria (3), archaea (3, 30), and mammals (1, 38, 41), including humans (13). As proposed by Challenger, the biomethylation of selenium and tellurium follows the same mechanism as arsenic but, in general, studies investigating these processes are rather rare (16,22,38). Mercury biomethylation, on the other hand, has been studied in more detail because of poisonings by methylmercury compounds (4,8,29,33). Although stibine has been implicated as a cause in sudden infant death syndrome (31), up to now, only trimethylantimony was detected as a biovolatilization product of antimony in the headspace of soil samples (24) and of pure cultures of Scopulariopsis brevicaulis (12,27). The biomethylation of inorg...