The history of the elucidation of the microbiology and biochemistry of
the oxidation of inorganic sulfur compounds in chemolithotrophic bact
eria is briefly reviewed, and the contribution of Martinus Beijerinck
to the study of sulfur-oxidizing bacteria highlighted. Recent developm
ents in the biochemistry, enzymology and molecular biology of su!fur o
xidation in obligately and facultatively lithotrophic bacteria are sum
marized, and the existence of at least two major pathways of thiosulfa
te (sulfur and sulfide) oxidation confirmed. These are identified as t
he 'Paracoccus sulfur oxidation' (or PSO) pathway and the 'S(4)interme
diate' (or S4I) pathway respectively. The former occurs in organisms s
uch as Paracoccus (Thiobacillus) versutus and P. denitrificans, and po
ssibly in Thiobacillus novellus and Xanthobacter spp. The latter pathw
ay is characteristic of the obligate chemolithotrophs (e.g. Thiobacill
us tepidarius, T. neapolitanus, T. ferrooxidans, T. thiooxidans) and f
acultative species such as T. acidophilus and T. aquaesulis, all of wh
ich can produce or oxidize tetrathionate when grown on thiosulfate. Th
e central problem, as yet incompletely resolved in all cases, is the e
nzymology of the conversion of sulfane-sulfur (as in the outer [S-] at
om of thiosulfate [S---SO3-]), or sulfur itself, to sulfate, and wheth
er sulfite is involved as a free intermediate in this process in all,
or only some, cases. The study of inorganic sulfur compound oxidation
for energetic purposes in bacteria (i.e. chemolithotrophy and sulfur p
hotolithotrophy) poses challenges for comparative biochemistry. It als
o provides evidence of convergent evolution among diverse bacterial gr
oups to achieve the end of energy-yielding sulfur compound oxidation (
to drive autotrophic growth on carbon dioxide) but using a variety of
enzymological systems, which share some common features. Some new data
are presented on the oxidation of S-35-thiosulfate, and on the effect
of other anions (selenate, molybdate, tungstate, chromate, vanadate)
on sulfur compound oxidation, including observations which relate to t
he roles of polythionates and elemental sulfur as intermediates.