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Based on testing the trace elements of the four main aquifers of underground water in Huaibei Coalfield by using the ICP-MS in the University of Science and Technology of China(USTC), the relation of trace elements of the four main aquifers was analyzed by using maximum correlation coefficient method. The study indicates that the different aquifers posses respective microelement distributional characteristics, which caused with average contents of trace elements in the different aquifers are related to the pH of the underground water and the contents of trace elements of the wall rock source in the research area, so researching on the distribution of geographic space and the change trend of hydro-geochemical character of different aquifers and the relation of the geologic environment and the trace elements conduce to establish the disciminand model of water inrush source.