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The difference is that Morellino di Scansano designates a DOCG red wine with fairly precise rules, while Maremma Toscana is a broader DOC, covering several styles and colors. Morellino comes from an area around Scansano, in the province of Grosseto, and must contain at least 85% sangiovese. The rest can be made up of other red grape varieties permitted in Tuscany.
On a «Maremma Toscana» bottle, you can find red, rosé or white, as a blend or under the name of a grape variety such as vermentino, sangiovese or cabernet sauvignon. The appellation therefore leaves more choice to the producer; look at the grape variety and the vintage to know what you are buying. The zones partly overlap, but the names are not interchangeable: a wine from the Scansano area can fall under Morellino if it meets its specifications, or carry the Maremma Toscana appellation if it is made according to the rules of that DOC. For a red typically linked to Scansano, choose Morellino; to compare varied styles from the province, look for Maremma Toscana.
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