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To taste the new oil, aim for frantoios between late October and December, especially in Maremma and in the Valdichiana : that's when you have the best chance of tasting it fresh out of the mill. At Scansano, the "Dalle olive all'olio" experience combines harvesting, a mill tour and bruschetta with new oil; the listed price is 55 € per adult. You must book, and the harvest depends on how the season is progressing: call before going.
In Alta Maremma, around Roccatederighi, Casa Julia offers comparative olive oil tastings; count on 25 € for this package, by reservation. Further east, in Sarteano, the Frantoio Tistarelli indicates a milling period from October 20 to December 20 and then offers to taste its "olio novello" on bread; the simple tour with tasting is listed at 15 € per person, by reservation. In practice, I would rather aim for November : in October, the harvest and the availability of new oil vary depending on the olives and the weather. Explicitly ask whether the oil served is really from the current harvest, and not an oil from the previous year.
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