Major ions were analyzed for twenty five groundwater samples collected from diverse aquifer in Baishan mining, northern Anhui province, China. Conventional graphical and multivariate statistical approach were completed to identify the hydro-geochemical process and water-rock interaction, that be combined with the Cluster Analysis (CA) and Fisher discriminant analysis to recognize the sealed samples, the result showed: the diverse samples have vary ions inheriting from aquifer, samples collected from Sandstone aquifer (SA) is characterized by the high concentration of Na+ + K+, for the feldspar weathering is dominant; Ordovician limestone aquifer (OA) waters have abundance Ca2+ and Mg2+, for the dissolution of calcite and dolomite obviously; the dissolution of calcite and other calcareous concretions are dominant in Taiyuan formation water (TA) and Quaternary aquifer (QA) for the high ratio of Ca2+/Mg2+, otherwise the varied content of SO42– and HCO3 could distinguish the two aquifer water. Twenty five groundwater samples, containing six sealed samples, had been subdivided in to four groups by the CA, what are corresponded with four aquifers. Fisher discriminant functions were obtained and the efficiency was acceptable for the error rate 4% in all twenty five samples.

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