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Sacked Anglo American Platinum mineworkers marched to the regional office of the National Union of Mineworkers in Rustenburg on Wednesday to cancel their membership.
One of the workers' leaders, Gaddafhi Mdoda, says they do not want the NUM to represent them, and see the union as the stumbling block to re-opening the wage negotiations.
However, there was no-one at the NUM office when they arrived.
Mdoda says they will march to the office again.
Police spokesperson, Captain Dennis Adriao, says the group gathered in the CBD without a permit.
