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Rousseff is expected to reach the Congress building at 3 p.m. (1800 GMT), where she will take the oath of office and deliver an address to the nation.
Delegations from 70 countries and major international organizations are expected to attend the ceremony, including Chinese Vice President Li Yuanchao and US Vice President Joe Biden.
Prior to that, Rousseff is set to ride in an open-top vehicle from Brasilia’s Cathedral to the National Congress, escorted by police motorcade.
Afterwards, she will be greeted with a 21-gun salute, before heading to the presidential Palace of Planalto to address the nation and receive the oaths of office from 39 members of her cabinet.
The ceremony will conclude with a reception at the Itamaraty Palace, headquarters of Brazil’s Foreign Relations Ministry.
Brazil’s relationship with the US has been strained after whistleblower Edward Snowden’s revelations the Obama administration spied on Rousseff. The Latin American economy has, instead, boosted ties with the BRICS with China now Brazil’s biggest trade partner.
Rousseff is 3rd in the list of Forbes most powerful women in the world and holds the number 31 spot in the Forbes list of the world’s most powerful people.
Security on Thursday has been heightened in the city of Brasilia with 4,000 policemen to be deployed in case of protests, and police barricades to be set up along the president’s route and at Planalto.
Security forces went through a rehearsal Sunday at the National Congress, though authorities said no major demonstrations are expected.
The Brazilian government expects 10,000 people to gather for Rousseff’s inauguration, while the ruling Workers’ Party (PT) estimates as many as 30,000 people may converge to the capital from different parts of the country.
Leftist Rousseff’s victory means another four years in power for the Workers’ Party, which has held power for 12 years and leveraged an economic growth to expand social welfare programs and lift more than 40 million from poverty in Latin America’s most populous country.
In her second presidential term, Rousseff will face severe challenges, particularly in countering a sluggish economy.
TBP and Agencies