The Valdarno, or Arno valley, is a geographical region that has nothing to do with the Maremma. It is a dense industrial and residential area, north of Siena, stretching towards Florence. If you are travelling in the Maremma, you will only cross the Valdarno if you arrive from the north and immediately continue onto the A1 motorway towards Rome. Avoid it for your stops, there is no major tourist interest and the atmosphere is very different from the authentic Maremma.
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