Both tested positive for methylhexanamine with A and B samples.
Evi Sachenbacher-Stehle, who won gold in 2002 and 2010, finished fourth in two events this year.
Police officer William Frullani, 34, will be replaced in Saturday’s four-man event by Samuele Romanini.
He is a former international decathlete, who competed at the 2006 European Championships.
It is Evi Sachenbacher-Stehle’s drugs test which is the bigger news, having won gold in the team sprint in the last Olympics in Vancouver and in the 4x5km in Salt Lake City.
“This is the worst nightmare you could imagine. I can’t explain how the doping test could be positive,” the 33-year-old said.
German Olympic Committee secretary general Michael Vesper said: “We stand for a doping-free sport and a zero tolerance.
“We only want clean performances. Every doping case is initially a disappointment but also proof that the system works.”
Before the Games, Russian biathlete Irina Starykh, who was a medal hope for the hosts, withdrew after failing a drugs test.
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