Obama noted the agreements mark another step in widely engaging with Latin America. He called Brazil—one of the up-and-coming emerging economies—a "major global player" crucial to collaboration on international issues.
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Rousseff stressed that cooperation will help Brazil work through a recent growth slog.
The measures are designed to "boost trade and investment that creates jobs for our peoples," Obama said. The steps include "ambitious goals" on reducing emissions and making renewable energy a 20 percent share of power use by 2030.
They also agreed to take steps so that Americans and Brazilians can travel between the two countries without visas and to allow Brazilians to apply for expedited "global entry" clearance when visiting the United States in early 2016.
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Rousseff also touched on the National Security Agency's spying program, which was revealed to have gathered data on her and Brazilian citizens. She confirmed that it caused her to cancel a past diplomatic visit, but said Obama has her trust now.
She added that Obama can "pick up the phone" if he wants non-public information from Brazil.
--Reuters contributed to this report.