The Etruscans were the first to benefit by the therapeutic effects of the waters of Caldana. It is probable that the springs fed the ancient Aquae Populoniae [Baths of Populonia]. In the Middle Ages they were still utilised, although the structures were no longer as efficient as in ancient times .

"There are most abundant and perennial springs of water, clear and constantly warm, which gush from the edges, and from the bottom of a grandiose basin on the southern side of the hill of Campiglia... Their effluent puts in motion various millstones, and was used for many years by an abandoned forge in processing iron brought from the Island of Elba". It was thus that Emanuele Repetti described Caldana a little before the middle of the 19th century, linking the water, used by the people of Maremma to treat sours and arthritic pains, to the metallurgical activity carried out in the area. Campiglia was, in fact, involved in the processing and refining of iron at least up to the end of the 18th century when, due to impoverishment of the woods and the consequent scarcity of wood, the plants were closed.

Dating from 1883 is the construction of the first modern thermal establishment, called Bagni Caterina. At Venturina today we find the Bagni del Sole thermal centre, with modern facilities and, about a kilometer away, the "Calidario", a fascinating warm-water swimming pool. In the past, the water of the "Calidario" furnished energy for the machinery of an iron-foundry and, later, for that of a paper mill.