Valentin also said he has resigned from the French football federation, saying he was fed up.
"It's a scandal for the French, for the young people here. It's a scandal for the federation and the French team," Valentin said. "They don't want to train. It's unacceptable.
"As for me, it's over. I'm leaving the federation. I'm sickened and disgusted," said Valentin, who walked away from the training field, got into a car and drove off.
The latest chaotic scene comes a day after Anelka was kicked off the World Cup team for a profanity-laced tirade against Domenech, whose tactics and management skills have been called into question.
The team arrived at training as usual Sunday and got off the bus to greet fans, but Domenech and France captain Patrice Evra stayed on the bus longer to talk.
When Domenech and Evra finally disembarked, fitness coach Robert Duverne was on the field putting down training cones. Evra then got into an argument with Duverne and Domenech walked over to intervene. Duverne then stormed off, throwing his accreditation badge to the ground.
Evra then handed a letter to the press officer, and the players, en masse, boarded the team bus and drew the curtains. The bus has yet to leave the area.
Domenech is expected to read a statement shortly.
About 200 fans soon started walking away.
In their first two matches at the World Cup, France drew 0-0 with Uruguay and then lost 2-0 to Mexico. France can still advance to the round of 16 with a win over host South Africa, as long as Uruguay and Mexico don't draw in the other Group A match.
