Being stratiform or stratoid, the Huangboshuwan witherite deposit at Zhiyang and the Wenyuhe witherite-barite deposit at Zhushan occur in the lower Lower Cambrian siliceous rocks and the orebodies are remarkably controlled by lithological character and petrography. Carbon and oxygen isotopic studies of witherite, barytocalcite and calcite have shown that the carbon, involved in the formation of these minerals, was derived largely from organic carbon resultant from degradation, polycondensation and dehydroxylation of bio-organic matter in sediments at the early stage of diagenesis. Extensive occurrence of bio-barite strongly evidenced that Ba2+ was concentrated and settled down in the form of bio-barite on the seafloor as a result of biological processes, thereafter forming the initially enriched orebodies of barium deposits. The witherite was metasomatic products of bio-barite under the action of sulfate-reducing bacteria and organic and inorganic reduction.