The groundwater discharge and heavy metal concentrations (Mn, Pb, Cu and As) at the outlet of Nanshan Laolongdong karst subterranean river, located at the urban region in Chongqing, were observed during the rainfall events. Analysis of flow and concentrations curves was employed to study their responses to the rainfall events and explore the internal structure of karst hydrological system. Principal component analysis (PCA) and measurements were used to identify the sources of heavy metals during rainfall. The result showed that the discharge and concentrations of the heavy metals responded promptly to the rainfall event. The variation characteristics of flow indicated that Laolongdong subterranean river system belonged to a karst hydrological system including fractures together with conduits. Urban surface runoff containing large amounts of Mn, Pb and Cu went directly to subterranean river via sinkholes, shafts and karst windows. As a result, the peak concentrations of contaminants (Mn, Pb and Cu) flowed faster than those of discharge. The major sources of water pollution were derived from urban surface runoff, soil and water loss. Cave dripwater and rainwater could also bring a certain amount of Mn, Pb and As into the subterranean river. Urban construction in karst areas needs scientific and rational design, perfect facilities and well-educated population to prevent groundwater pollution from the source.
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