Barium (Ba) is a toxic element and can cause serious health effects. Humans have experienced increased exposure to Ba due to its intensive usage in industrial areas and daily life. Anthropogenic activities of Ba mining and the manufacture of Ba containing products introduce the element into surrounding areas, posing environmental concerns. Concentrations of total Ba (TBa) and dissolved Ba (DBa) in water samples collected from active Ba mines in Tianzhu, east Guizhou Province, southwestern China were measured to show the regional dispersion of Ba contamination. Aqueous Ba species in water were calculated using the PHREEQC program. The results showed that TBa and DBa concentrations ranged from 6.7 to 483.1 mu g/L and from 7.5 to 222.7 mu g/L, respectively. TBa concentrations presented a high average value of 126.6 mu g/L and greatly exceeded the reported common value of 10 mu g/L Ba in surface water set by the Ministry of Environment Protection of China. PHREEQC results indicated that Ba species in water were present as Ba2+, BaSO4, BaHCO3, BaCO3, and BaOH+. The distribution of Ba species in water is controlled by pH and total organic carbon (TOC), and the lower pH (pH < 7) the higher the dissolved fractions. The log K-d values (K (d) , dissolved-particulate distribution coefficients) varied from 2.41 to 6.32. Significant correlations were observed among Ba2+ and K+, Na+, Cl-, NO3-, with Pearson correlation coefficients of 0.425, 0.531, 0.853, 0.612, and 0.329, respectively (p < 0.01). Elevated Ba concentrations in water indicated that the Ba contamination and its distribution pattern in local aquatic ecosystems are derived from Ba mining sites in the Tianzhu area.