A Wednesday of Olympic woe was compounded by the elimination of the Football Ferns from the women's tournament.
New Zealand needed at least a draw against France in their final match to be guaranteed a place in the quarter-finals, but lost 3-0.
France scored their first goal late in the first half to take a psychological edge into the break, then extended their lead 18 minutes into the second half and late on with an injury time penalty.
Other results did not go the Ferns way and coach Tony Readings said they were left bitterly disappointed.
"We had chances and we've got to take them... no matter what you do and how you play, that's always going to make it hard," he said.
Earlier this morning, the three-day eventing team led by Sir Mark Todd missed out on gold after he knocked over four rails in the final session.
If he had knocked down just one rail New Zealand would have won gold.
In rowing, Mahe Drysdale and Emma Twigg went through as expected, but both the men's and women's double sculls teams fell.
The men's pair of Hamish Bond and Eric Murray are through to the finals after posting the fastest overall time in their semifinals, while the men's lightweight four are also through.
The men's sevens side also got off to a disastrous start, losing 14-12 to Japan.
In a double blow for the team, Sonny Bill Williams was ruled out of the tournament with a partial Achilles rupture.
New Zealand did thrash Kenya 28-5 in their next game, but still need to beat Great Britain tomorrow and rely on other results to make the knockout stages.
The men's hockey team also suffered a loss, going down 3-2 to Spain.
It was 2-2 at half time with the Spanish scoring the winner late in the game.
Simon Child scored both goals for New Zealand.
The Black Sticks men have already lost to Australia and drawn with Great Britain.
They have remaining games against Brazil and Belgium and will probably have to win both of those games to make the quarter-finals.
Meanwhile, sailor Josh Junior didn't have a great opening day in the Finn class, scoring an 18th and a disqualification in his two races and is 21st overall.
But there was more positive news in the Laser class, with New Zealand's Sam Meech improving to third overall after four races.
Meech scored a 5h and a 6th in his two races today and he's now seven points behind the leader from Argentina.