Thank you sydneynick, I still haven't managed to understand why some links get automatically shortened by the TA site, and others remain unwieldy.
Just for confirmation, I had also checked the DB Bahn site which has been reported to *sometimes* have slightly different information, but it shows no 6:18am train from Mestre to any of the Florence stations either.
The fact that there is a train arriving AT Florence at exactly 6:18 (well, scheduled to at least) would lend me to think that the OP may be misreading the Italian language ticket, something that, with Trenitalia's usual twisted logic, is not at all particularly difficult to do.
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