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The Castañar Cave (central western Spain) formed in mixed carbonate–siliciclastic rocks of Neoproterozoic age. The host rock is finely bedded and shows a complex network of folds and fractures, with a prevalent N150E strike. This structure controlled the development and the maze pattern of the cave, as well as its main water routes. The cave formed more than 350 ka ago as the result of both the dissolution of interbedded carbonates and weathering of siliciclastic beds, which also promoted collapse of the overlying host rock. At present it is a totally vadose hypergenic cave, but its initial development could have been phreatic. The cave's speleothems vary widely in their morphology and mineralogy. In general, massive speleothems (stalactites, stalagmites, flowstones, etc.) are associated with the main fractures of the cave and bedding planes. These discontinuities offer a fairly continuous water supply. Other branching, fibrous, mostly aragonite speleothems, commonly occur in the steeper cave walls and were produced by capillary seepage or drip water. Detailed petrographical and isotope analyses indicate that both aragonite and calcite precipitated as primary minerals in the cave waters. Primary calcite precipitated in waters of low magnesium content, whereas aragonite precipitated from magnesium-rich waters. Differences in isotope values for calcite (−5.2 ‰ for δ18O and −9.6 ‰ for δ13C) and aragonite (δ18O of −4.5 ‰ and δ13C of −3.5 ‰) can be explained by the fact that the more unstable mineral (aragonite) tends to incorporate the heavier C isotope to stabilize its structure or that aragonite precipitates in heavier waters. Changes in the water supply and the chemistry and instability of aragonite caused: (1) inversion of aragonite to calcite, which led to the transformation of aragonite needles into coarse calcite mosaics, (2) micritization, which appears as films or crusts of powdery, opaque calcite, and (3) dissolution. Dolomite, huntite, magnesite and sepiolite were identified within moonmilk deposits and crusts. Moonmilk occurs as a soft, white powder deposit on different types of speleothems, but mostly on aragonite formations. Huntite and magnesite formed as primary minerals, whereas dolomite arose via the replacement of both huntite and aragonite. Owing to its variety of speleothems and location in an area of scarce karstic features, the Castañar Cave was declared a Natural Monument in 1997 and is presently the target of a protection and research programme. Although the main products formed in the cave and their processes are relatively well known, further radiometric data are needed to better constrain the timing of these processes. For example, it is difficult to understand why some aragonite speleothems around 350 ka old have not yet given way to calcite, which indicates that the environmental setting of the cave is still not fully understood.