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Although similar geochemical behaviors of arsenic (As) and antimony (Sb) in the environment has been assumed and widely reported, growing evidence suggests the two elements cannot, under some conditions, be assumed to behave similarly. In this four-year study (samples collected in each year), comparative investigation of the biogeochemistry of As and Sb in water/fish, soil/vegetable, tailings/plant samples were carried out at the world's largest active Sb mine area (Xikuangshan, China). Depending on duration the tailings had been stacked, significant differences in spatial distributions between As and Sb were found, and these were associated with change in pH over time. Bio-accumulation factors (BAFs) of As were approximately 10-fold greater than those of Sb in fish/water, plant/tailing, and vegetable/soil systems. Sb had higher BAF in non-fatty tissues such as gills of fishes and shells of crabs. BAFs of Sb in vegetable/soil exhibited insignificantly, but different from As, positive correlation with pH in soil. [ABSTRACT FROM AUTHOR]