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Some international car hire companies in downtown Pisa close at 13.00 until 16.00.
The so-called 24 hour API self service filling station at Pisa Airport closes from 13.00 to 15.30 and the instructions for self service are only in Italian. From a distance the sign at the filling station shows credit cards but there is no facility when the staff are absent to pay by credit card.
Italy is still great but be aware of the lunchtime closing problem.