#32 is listed as the Libero & as one of the starting 6 players (no one caught it until start time). So #32 must play as the Libero with a legal Libero uniform, etc. Is the infraction an inaccurate line up & therefore a point & service to the opponent?

Answer: After the line-up has been accepted by the second referee and scorer, player #32 is the only player for that team who may play as a Libero for the match. A “phantom” substitution must be made for the #32  “regular” player.   No other penalty will occur.

However, the second referee and scorer could have prevented this situation when the line-up was submitted by looking it over and noticing that a player number was listed in two positions on the line up sheet.   The second referee could have then asked the coach or captain to correct the error before the line-up was recorded on the scoresheet.