Miguel Macedo resigned following an investigation into alleged corruption linked to residence permits.
Venezuela, Angola, Malaysia, New Zealand and Spain awarded non-permanent seeats.
Thousands turned out for the one-year anniversary of the killing of a rapper by a far-right party supporter.
Prime Minister Manuel Valls forestalled a rebellion within the Socialist government in a tight confidence vote.
Center-left party faces tough task of cobbling together majority without conceding to Sweden's fringe parties.
Wednesday marked the last day of campaigning as voters mulled whether to say "Yes" or "No".
The U.K. party leaders will be campaigning in Scotland for a referendum "No" vote.
The prime minister's visit comes as polls show Scotland split over independance from Great Britain.
Kiev has rejected calls from Moscow to negotiate with pro-Russia separatists, calling them "terrorists."
An informal vote on independence for Catalonia has shown more than 80% in favour, officials say.
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