Playing catch-up finally caught up with the Hockeyroos, with their Olympic Games medal hopes over.
A 0-0 draw with Argentina on Monday wasn't enough to get Australia into the women's hockey semi-finals, with a win the only way they could progress.
Instead Argentina top Pool B, with New Zealand going through to the medal rounds in second place.
Australia finish third in the group, and now play a fifth versus sixth classification match on Friday to end their Olympic campaign.
Argentina needed just a draw to qualify going into the game, and the Hockeyroos' need for all three points prompted a high octane start.
Megan Rivers forced a great save from Argentine goalkeeper Florencia Mutio after just three minutes, but otherwise it was a tense, midfield dominated first half.
More of the same followed in the second half, with Argentina creating the better chances and their defence giving the desperate Hockeyroos no change.
Australia did not manage one penalty corner for the match.
The Hockeyroos even subbed out goalkeeper Toni Cronk in the last three minutes to add an extra outfield player to snatch a winner.
But like the rest of the match, the last few minutes and Argentina's quality defence proved engrossing, but ultimately frustrating for Australia.
Earlier the Netherlands remained undefeated in their fifth and final group match to top Pool A with a 2-1 win over Great Britain.
Dutch stars Naomi Van As and Kitty Van Male netted in the second half to erase a one-goal deficit, but Great Britain still qualified for the semi-finals in second spot.
Argentina now play Great Britain in Wednesday's semi-finals, with New Zealand, who beat Germany to book their spot earlier on Monday, taking on the Dutch in the other semi.