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Karpenisi is the capital of the prefecture and is located at the foot of Mount Velouhiou (2312 meters). Mountains in Karpenisi is Agrafa, Chelidona, Kaliakouda, Panaitoliko, Neraidovouni. Rivers are the Karpenisiotis the Trikeriotis, Achelos, Agrafiotis, the Taropos and Krikelopotamos. Canyons are Pantavrechi, Black Cave, Vothona, Vinianis and Krikelopotamos. Karpenisi is located 295 km away from Athens, 370 km away from Thessaloniki, 75 km away from Lamia and 110 km away from Agrinio.

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