In this paper, the concentrations of Cu, Mg, Zn and Cd elements in the mixture solution consing of CuSO4, Mg(NO3)2, Zn(NO3)2 and Cd(NO3)2 were measured with Laser Induced Breakdown Spectroscopy with aqueous jets which were generated within 1 064 nm wavelength of Nd: YAG laser with pulse width of 10ns and repetitive rate of 10 Hz. The mixture solutions of seven different concentrations consist of Cu, Mg, Zn and Cd were compound by adding the four solutes to the distilled water. The LIBS experiment date have been treated with the statistical exploratory data analysis method to abtain calibration curves of Cu, Mg, Zn and Cd elements, whose linear fitting coefficient R2 were all above 099, the LOD of Cu, Mg, Zn and Cd elements were determined as 562, 471, 1367 and 443 ppm, respectively. The LOD of Cu element was 398 ppm for pure CuSO4 solution with better experimental results than that of mixed solution, Finally, the LIBS detected differences were analyzed. The research results show that LIBS has a promising application in detecting heavy metal elements in the environmental wastewater pollution．