Juan David Ortiz, a 35-year-old intel supervisor with the Border Patrol, is charged with four counts of murder for the string of killings that began on September 3.
Juan Davis Ortiz, 35, a former US Navy vet, who has been with the US Border Patrol for 10 years was captured by the state troopers on Saturday in Laredo, a Texas city on the border with Mexico.
According to the affidavit, Ortiz told investigators that after Pena ran off, he picked up his last two victims, whose identities have not yet been released by authorities. He said all of the women worked as prostitutes.
The names of the victims have not been released, but Alaniz says two are US citizens.
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She then described the suspect to the officer and provided details about his vehicle and his home, Alaniz said.
Webb County Sheriff Martin Cuellar said at a news conference that the agent, Juan David Ortiz, was arrested early Saturday morning.
The federal agency issued a statement offering its "sincerest condolences" to the victims' families and saying criminal activity by its employees is not tolerated.
The bodies of two of the women were discovered this month along Interstate 35 in rural northwest Webb County, the Laredo Morning Times reported, while the third and fourth were found in the same area this weekend.
Andrew Meehan, a senior US Customs and Border Protection official, said in a statement that the agency was co-operating fully with investigators.
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"I extend my condolences to the families of the victims during this hard time".
The arrest of a veteran Border Patrol agent as a serial murder suspect in the shooting deaths of four people has rocked the border community of Laredo. Investigators say Ortiz is believed to have been acting alone.
Authorities found Ortiz at a gas station in Laredo, about 160 miles southwest of San Antonio.
The next two killings occurred in the hours after the woman escaped early Saturday, authorities said.
Cueller thanked the Department of Public Safety, the Texas Rangers and the district attorney's office for their assistance in the investigation.
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