At around the same time, two people were hospitalised after being exposed to a white powder that was contained in mail sent to Sen. Ted Cruz's Houston campaign office. Their injuries are not known. Neither of the victims worked for Cruz's campaign.
It is not known if the two incidents are linked or what the substance sent to Cruz's office was.
All mail sent to the Pentagon via the US Postal Service on Monday was placed under quarantine as a precaution and all workers from Cruz's Houston campaign office were evacuated.
CNN cited two unnamed officials who named Mattis and Richardson as the intended targets of the Pentagon mail.
"The Pentagon Force Protection Agency detected a suspicious substance during mail screening at the Pentagon's remote screening facility.
"The envelopes were taken by the FBI this morning for further analysis," spokesman Col. Rob Manning said in a statement.
All mail that was sent to the Pentagon was placed under quarantine as a precaution.
Ricin exposure can lead to death if the toxin is inhaled directly. It is commonly used in terror plots and is found in castor beans.
It remains unclear what form it was sent to the Pentagon in.
In a statement, the FBI confirmed its investigation.
"On Tuesday, October, 2, 2018, in coordination with the Pentagon Force Protection Agency, FBI Special Agents took possession of two suspicious envelopes that had been screened at the Pentagon mail facility.
"Those envelopes are currently undergoing further testing.
"As this is ongoing, we will have no further comment," a spokesman said.
Ricin causes a painful deaths which begin with nausea and vomiting.
The toxic components then cause internal bleeding and ultimately lead to respiratory failure.
Several terror plots which use the toxin have been foiled in Europe in the past including an intended attack on a London Underground station in 2003 and a separate attack in Germany in June this year.
After initial exposure to ricin, symptoms ordinarily appear in around 10 hours and death can occur within 72 hours.
Since the anthrax attacks which killed five people after the powder was distributed through mail in 2003, the US Government has increased measures to protect workers and officials from exposure to any harmful substances.
They include putting mail through X-Ray machines and scanners which detect vapours and identify anything poisonous or toxic.
In Washington DC, the US Postal Service also samples the air as mail is being sorted before it is sent to government buildings.