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Hangjinhouqi is one of the most serious endemic arsenic and fluorosis areas in Hetao Plain, China. Groundwater samples (n=97) and two sediment cores issued from boreholes were collected to characterize the hydrogeochemistry of groundwater and sediment lithology of aquifers. Results showed that arsenic and fluoride content in groundwater range from 1 to 1093 mu g/L and from 0.30 to 6.01 mg/L, respectively. The highest concentrations are mainly found in the flat areas of the Yin Mountains. As and F are not correlated, suggesting that their origin and/or geochemical processes leading to their release to groundwater are different. Between 15 and 45m of depth, both arsenic and fluoride are more easily released into groundwater. The external environment of high As and high F groundwater formation consisted of a lake-based geographical environment in a long term and closed geological structure, arid and semi-arid climatic conditions, as well as hydrogeological characteristics. (C) 2012 The Authors. Published by Elsevier B.V.