Adm. Thad Allen also announced the deaths of two people involved in the cleanup operation.
The accident came on the day BP's Bob Dudley took over from CEO Tony Hayward as the company's point man for the spill.
The accident at BP's fractured well caused gas to rise through the vent that transmits warm water down to prevent the formation of ice-like crystals in the cap, Allen said. The cap has been removed to determine whether any such crystals have formed. On Wednesday night, BP was working to replace the cap.
The cap "has been moved off the Deepwater Horizon's failed blowout preventer to ensure the safety of operations and allow the unexpected release of liquids to be analyzed," according to the cleanup's official website.
In the 24 hours before being removed, the cap collected 700,000 gallons of oil.
The Deepwater Horizon drilling platform exploded April 20, killing 11 workers on board and rupturing an oil well 1,500 meters below the surface of the water.
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Estimates differ as to how much oil has leaked, with one government study putting the figure at as much as 1.2 million gallons a day.
BP has agreed to set aside $20 billion in an escrow fund for cleanup and compensation of those affected by the massive spill. The company's stock has tumbled since the accident, and credit rating agencies have downgraded its rating.
Allen said one of the two cleanup-related deaths occurred during an accident "regarding a swimming pool." The other person killed was a vessel operator, he said.
"Our thoughts and prayers go out to their families," Allen said. "We know this is a devastating thing to happen."
Allen did not provide further details, but police in Gulf Shores, Ala., said they are investigating the death of a 55-year-old man whose body was found in his boat. The man appears to have shot himself in the head, police said.