Canadian Pacific will appeal the decision, a spokesman for the company said on Thursday.
Quebec has added Canadian Pacific (CP) to a legal list of companies it is ordering to help cover the clean-up and decontamination after the train derailed and blew up in the eastern town of Lac-Megantic, spilling some 1.48 million U.S. gallons (5.6 million liters) of oil.
"As a matter of fact, and law, CP is not responsible for this clean-up. CP will be appealing," said spokesman Ed Greenberg.
The train was operated by Montreal, Maine & Atlantic (MMA), which filed for bankruptcy protection last week.
A Quebec government statement on Wednesday said CP was hired to transport the tanker cars of oil and had done a deal with MMA, which ran the rail line that passed through eastern Quebec.
"Our duty is to do all we can to ensure that the firms responsible for this accident bear the costs linked to the clean-up and decontamination," Environment Minister Yves-Francois Blanchet said in the statement.
Canada announced on Tuesday it would shut down MMA on August 20, saying the firm did not have enough insurance.
In a court filing, MMA said its insurance covered liabilities up to C$25 million ($24.2 million), while clean-up costs could exceed C$200 million.
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