Marta left the field in tears after being sent off for a dangerous high tackle during Brazil's 2-0 defeat to Spain in their final Group C game at the Olympics.
The Brazil great narrowly missed Olga Carmona's head with an out-of-control attempt to reach the ball in first-half stoppage time, receiving a straight red card in what could turn out to be her final-ever Olympic game.
Brazil needed a win to secure a place in the knockout rounds, but now they face a nervous wait to see if they will be one of the two best third-place teams in the last eight – a match they would have to play without their captain.
Athenea del Castillo eventually got the breakthrough after 68 minutes, before Alexia Putellas scored in the 107th minute to ensure they stayed perfect to top the group.
It was a dominant performance by La Roja, who created an expected goals tally of 2.75 from 27 shots compared to Brazil's 0.3 from 10 efforts.
Spain will face the best third-place team from either Group A or B in the quarter-final on Saturday.
Meanwhile, Japan also secured a spot in the knockout rounds with an emphatic 3-1 victory over Nigeria.
Japan stunned Brazil in the second group game and continued their momentum by getting the job done in the first half.
Maika Hamano and Mina Tanaka put them 2-0 up before Jennifer Echegini pulled one back for Nigeria.
However, Hikaru Kitagawa's strike just before the break restored Japan's two-goal cushion and held onto that lead to set up a meeting with the winners of Group B in the next round.
Jurgen checks out? Klopp drops retirement hint
Jurgen Klopp has suggested he is more likely to retire than step back into management.
Klopp left Liverpool at the end of last season, and is enjoying a sabbatical away from the game.
The German had been linked with the vacant England job, but has distanced himself from such speculation, while he also reportedly turned down an offer to coach the United States.
And now the 57-year-old, who coached Mainz before leading Borussia Dortmund to back-to-back Bundesliga titles, has claimed, for the time being, he is considering himself as retired, though he did leave the door open to return to football in some capacity.
"Let's see what it will look like in a few months. Nothing is coming through at the moment," Klopp said.
"As of today, that's it for me as a coach. I didn't quit on a whim, it was a general decision.
"I've also coached the best clubs in the world. Maybe we can talk about it again in a few months.
"I still want to work in football and help people with my experience and contacts. Let's see what else there is for me."
Klopp has won 13 major honours during his managerial career, but enjoyed his most success across his nine-year stint at Anfield.
The 57-year-old would lead Liverpool to eight major trophies, including their first Premier League title and their sixth success in the Champions League.
Of the three sides he managed, Klopp managed more games (491), oversaw more wins (299) and scored more goals (1035) during his Liverpool tenure.
Should this be the end for Klopp, he ends his managerial career having won 584 of his 1075 games in charge, averaging 1.87 points per game across his 23-year career.
Canada advance to Olympic quarter-finals despite points deduction
Canada advanced to the knockout stages of the Paris Olympics against all the odds following a 1-0 victory over Colombia in Marseille.
The defending Olympic champions had won both their group matches, but were docked six points after being found guilty of using a drone to spy on New Zealand's training session ahead of their opening match of the Games.
It subsequently saw head coach Bev Priestman banned from football-related activities for a year, and despite appealing the decision, saw it rejected.
However, Vanessa Gilles' header proved to be the difference as she rose highest to meet Jessie Fleming's corner kick delivery in the 61st minute.
While Canada only took three points from their group games, they joined both Spain and the United States as the only teams to win all their games at the tournament so far.
Colombia, who started the day's action in second, settled for third spot but advanced to the knockout stages as one of the best third-placed teams and will face Spain.
Canada, meanwhile, will continue their quest for a second Olympic triumph in the Parc des Princes on Saturday where they will face Germany.
In the other Group A fixture, hosts France confirmed their place in the knockout stages of the competition after a hard fought 2-1 triumph over New Zealand.
Marie-Antoinette Katoto scored the opening goal of the game in the 22nd minute, only for Kate Taylor to respond for the visitors two minutes before the interval.
Katoto, who scored a brace against Colombia in their opening group game, notched her second double of the tournament late on to take her tally to five at the Games and secure top spot for the French.
France will next be in action this Saturday in Nantes, where they will face Brazil, who will be without veteran striker Marta following her red card against Spain earlier in the day.
Gauff endures doubles disappointment at Paris Olympics
Coco Gauff suffered back-to-back defeats in her respective doubles matches as her hopes of an Olympic gold medal were dashed at Roland-Garros.
In her first game of the day, Gauff teamed up with world number six Jessica Pegula to face Czech Republic duo Karolina Muchova and Linda Noskova.
After taking the first set, Gauff and Pegula were unable to continue their momentum, falling to a 6-2 4-6 5-10 defeat.
The American pairing started strongly and raced into an early lead, taking the opening set in what seemingly looked like a straightforward victory for Team USA.
However, Muchova and Noskova rallied and in a second set that saw five break points converted by both, the Czech's would prevail to take the game to a decider.
Gauff and Pegula lost four straight games to put their opponents in the ascendency, with Muchova and Noskova able to see out the win to progress to the quarter-finals.
Gauff emerged back onto the clay courts in the French capital for her mixed-doubles match soon after, joining Taylor Fritz to face a Canadian pairing of Felix Auger-Aliassime and Gabriela Dabrowski.
The American duo would come from a set down to take the game to a decider, but it would be their opponents who emerge 6-7 (2-7) 6-3 8-10 victors.
Gauff and Fritz exchanged blows with the Canadians, but were edged out in a first set tie-break after losing four games on the spin.
But not wanting to let their dreams of a medal die, the American pair would recover from losing an early break point to rally and earn one of their own in the eighth game, seeing out the win to take Gauff to her second third-set decider of the day.
However, the same result would transpire, with Auger-Aliassime and Dabrowski edging a nail-biting conclusion to book their place in the quarter-finals of the competition.
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