A television producer was also injured as police with riot shields attempted to quell unrest from citizens railing against Brazil's decision to host the tournament rather than spend extra funds on domestic issues.
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The incidents happened outside a subway station in the city just hours before Brazil take on Croatia at the Arena Corinthians on Thursday evening. The crowds also attempted to restrict movement on roads and footpaths leading up to the stadium, but were quickly moved along by the armed police ranks.
The trouble comes after a six-day subway strike in Sao Paulo was lifted just in time for the build-up to the opening fixture, while ground staff at many of Brazil's airports have voted to go ahead with 24-hour industrial action to coincide with the tournament's opening matches.
Brazil president Dilma Rousseff conducted an address to the nation on Tuesday asking the population to come together over the next month and postpone plans to disrupt the tournament, but the latest incidents have cast a shadow over the finals once more.