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As determined by transmission electron microscopy (TEM), the reduction of selenate and selenite by Desulfovibrio desulfuricans, a sulfate-reducing bacterium, produces spherical (Se, S) sub-micro particles outside the cell. The particles are crystalline or amorphous, depending on medium composition. Amorphous-like Se-rich spherical particles may also occur inside the bacterial cells. The bacteria are more active in the reduction of selenite than selenate. The Desulfovibrio desulfuricans bacterium is able to extract S in the (S, Se) solid solution particles and transform S-rich particles into Se-rich and Se crystals. Photoautotrophs, such as Chromatium spp., are able to oxidize sulfide (S2-). When the bacteria grow in sulfide- and selenide-bearing environments, they produce amorphous-like (S, Se) globules inside the cells. TEM results show that compositional zonation in the (S, Se) globules occur in Chromatium spp. collected from a top sediment layer of a Se-contaminated pond. S2- may be from the products of sulfate-reducing bacteria. Both the sulfate-reducing bacteria and photosynthetic Chromatium metabolize S preferentially over Se. It is proposed that the S-rich zones are formed during photosynthesis (day) period, and the Se-rich zones are formed during respiration active (night) period. The results indicate that both Desulfovibrio desulfuricans and Chromatium spp. are able to immobilize the oxidized selenium (selenate and/or selenite) in the forms of elemental selenium and (Se, S) solid solutions. The bacteria reduce S in the (Se, S) particles and further enrich Se in the crystalline particles. The reduced S combines with Fe2+ to form amorphous FeS.