Was Mary free from sin?

Irenaeus of Lyons c. 130–c. 202 ADAgainst Heresies 3.22.4

For what the virgin Eve bound by unbelief, the virgin Mary loosed by faith.

The sentence before this one says that the knot of Eve's disobedience was loosed by Mary's obedience: Eve, seduced, became the cause of death for the whole race, and Mary, believing the angel, became the cause of salvation. It is the earliest statement of Mary as the new Eve. This part of Against Heresies survives in its ancient Latin translation.

Origen of Alexandria c. 185–c. 254 ADHomilies on Luke 17.6–7

What are we to think? When the apostles were scandalized, was the mother of the Lord free from scandal? If she did not suffer scandal in the Lord's Passion, Jesus did not die for her sins. ... Yes, Mary too was scandalized at that time. ... The sword of unbelief will pass through you, and you will be struck by the blade of doubt.

On Luke 2:35, Simeon's sword. Origen argues from the Lord's word that all would be scandalized that night, Peter included, and from Romans 3:23, quoted in the homily, that all sinned and need God's glory: Mary, he says, was scandalized at the cross, and the sword that pierced her soul was unbelief and doubt. The homilies survive in Jerome's Latin translation; a Greek fragment of this passage also survives.

John Chrysostom c. 349–407 ADHomilies on Matthew 44.1, on Matthew 12:46–50

So here too he healed the disease of vainglory and gave his mother the honor due to her, though she asked at the wrong time.

Chrysostom thinks Mary and the brothers wanted to show their authority over Jesus before the crowd, as at Cana. Several Greek fathers spoke of Mary's faults this way.

Augustine of Hippo 354–430 ADOn Nature and Grace 36.42

Except, then, the holy Virgin Mary, about whom, for the honor of the Lord, I want no question at all to be raised when we are dealing with sins.

Pelagius had listed Mary among the sinless. Augustine agrees for her alone, asking how we can know what more grace she was given. He still held she was born with original sin. The Migne scan is poor here; the quote follows the standard text.