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Miners are disputing a bill under debate in parliament that would deny them the right to work for foreign companies, as opposed to just state-owned ones.
The toll of one miner dead was reported by Interior Minister Carlos Romero.
Mining officials said two miners were killed, but this could not be immediately confirmed.
Romero said many police were injured by blasts from dynamite sticks hurled by miners.
Protests began early in the day with highways blocked in the Andean mountain departments of La Paz, Oruro, Cochabamba and Potosi.