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Spain started at left-back after England’s group stage draw with Ghana ended in a goalless draw, and was replaced by wins over Croatia and Panama.
Chelsea captain James has missed the last two games due to a muscle strain suffered late in the game against Ghana.
The 26-year-old has yet to fully train with the team since the injury and is the only player absent for Saturday’s session in Mexico City.
The Football Association told BBC Sport that James was away from the training ground attending to his own personal programme.
Tuchel also told the media on Saturday that the player would need a late assessment before deciding whether he would be fit for the bench against Mexico.
Following Quassah’s injury, the German said he was concerned about England’s right-back crisis ahead of the Democratic Republic of Congo game.
Newcastle right-back Tino Livramento was forced out of the squad ahead of the World Cup with a calf problem, and Tuchel opted to call up Chelsea centre-back Trevoh Chalobah as a replacement for Trent Alexander-Arnold at right-back.
Tuchel’s only option at right-back is Ezri Konsa, who has started all four of England’s games so far at centre-back.
